Enhanced Fiber Additive; and Use

ABSTRACT

The disclosure provides a process of modifying a seed based fiber (SBF) to form an enhanced fiber additive (EFA). The process includes an acid treatment step and optionally at least one fiber modification step. Preferred EFA products and uses are described.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Divisional of U.S. application Ser. No.09/689,994 filed Oct. 13, 2000, currently pending, which is aContinuation-in-Part of U.S. application Ser. No. 09/419,438 filed Oct.15, 1999, now abandoned, the complete disclosures of which areincorporated herein by reference.

FIELD OF THE INVENTION

This disclosure relates to a method of processing plant seed basedfibers (SBF) to obtain an enhanced fiber additive (EFA); preferred EFA;and uses thereof.

BACKGROUND

Grains such as corn and soybeans are processed to separate out usefulcomponents such as protein, oil, starch, and seed fiber. The starch istypically modified to make products that are used in food and industrialapplications. The oil is typically refined and used as cooking and/orbaking oil. Soybean protein is typically processed as a food additive.Corn gluten protein is typically used as a feed ingredient in thepoultry industry. The seed fiber is typically used as a feed ingredientfor many pet foods and for bovine feed. However, it would be desirableto obtain a processed seed fiber that is suitable for other uses, forexample in papermaking and/or as a food additive for human consumption.

SUMMARY

This disclosure provides, among other things, methodology for processingseed based fiber to obtain an enhanced fiber additive. In typicalapplications, the method includes treating a seed based fiber with adilute acid solution. The typical dilute acid solution includes a strongor weak acid and an aqueous liquid or water. Preferably the acid is astrong acid such as hydrochloric acid or sulfuric acid. The seed basedfiber is preferably treated with the dilute acid solution for an amountof time sufficient to reduce the lignin content of the seed based fiber.The resulting fiber is sometimes referred to herein as an acid treatedfiber. The acid treated fiber can be washed, to remove the residual acidand impurities, and be dried to form an enhanced fiber additive. Hereinthe term “enhanced fiber additive” refers to a seed based fiber whichhas been enhanced by acid treatment in any of the general mannerscharacterized herein, regardless of whether other enhancements have beenperformed.

In preferred processing, the method includes treating an acid treatedfiber with a modifying agent. The modifying agent preferably includes anacid chlorite solution or a peroxide solution. A typical, preferred,acid chlorite solution includes an aqueous liquid, a strong acidselected from the group consisting of sulfuric acid and hydrochloricacid and a chlorite salt selected from the group consisting of sodiumchlorite, potassium chlorite, magnesium chlorite, and calcium chlorite.The typical, preferred, peroxide solution preferably includes hydrogenperoxide and an aqueous liquid or water. The acid treated fiber can betreated with either the acid chlorite solution or the peroxide solution,or both. The acid treated fiber is typically treated with the modifyingagent for an amount of time sufficient to improve the brightness of thefibers. The resulting fiber with improved brightness is also referred toas an enhanced fiber additive or as modified fiber. The modified fiberis typically washed to remove residual chemicals and impurities anddried to form a preferred brightened, enhanced fiber additive. In someinstances, the treatments lead to reduction in lignin content, as apercentage.

The disclosure also provides a method of making paper and a paperproduct. The paper is formed by processing wood to make wood pulp;combining the wood pulp with enhanced fiber additive to form a modifiedpulp, positioning the modified pulp on a screen; draining the modifiedpulp; pressing the modified pulp; and drying the modified pulp. The woodpulp can be prepared by either chemical or mechanical pulping. Thedisclosure also provides a paper product, which includes wood pulp andthe enhanced fiber additive. Alternate papers, including alternatefibers from wood, can also be made with the EFA.

The disclosure also provides a method of preparing a food product andthe resulting food product, wherein the food product is formed bycombining an ingredient (or ingredients) with the enhanced fiberadditive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a flow chart of methods for processing seed based fiber inaccord with the present disclosure.

FIG. 2 shows a digital printout of Scanning Electron Micrograph (SEM)taken at 100× of ground corn fiber (SBF-C) from a corn wet millingprocess.

FIG. 3 shows a digital printout of Scanning Electron Micrograph at 100×of the ground enhanced fiber additive from corn fiber (EFA-C) made inaccord with the present disclosure.

FIG. 4 is a Fourier Transform Raman Spectral comparison of SBF-C and theEFA-C.

FIG. 5 is a graph showing the burst strength of paper hand sheets withand without EFA-C (enhanced fiber additive from corn hulls).

FIG. 6 is a graph showing the tensile strength exhibited by paper handsheets with and without EFA-C.

FIG. 7 is a graph showing the burst strength of paper hand sheets withand without EFA-S (enhanced fiber additive from soy hulls) and EFA-W(enhanced fiber additive from wheat midds).

FIG. 8A shows a schematic of a WMU pilot paper machine.

FIG. 88 shows a typical paper machine.

FIG. 9 is a graph showing the burst strength of paper at two differentbasis weights made with and without the EFA-C.

FIG. 10 shows the Tensile strength of the paper at two different basisweights made with and without the EFA-C.

FIG. 11 shows the Tear strength of the paper at two different basisweights made with and without the EFA-C.

FIG. 12 represents the Scott Bond strength of the paper at two differentbasis weights made with and without the EFA-C.

FIG. 13 shows the Porosity of the paper at two different basis weightsmade with and without the EFA-C.

FIG. 14 shows the Bulk density of the paper at two different basisweights made with and without the EFA-C.

FIG. 15 shows the Fold Endurance strength of the paper at two differentbasis weights made with and without the EFA-C.

FIG. 16 shows the enhancement of Scott Bond internal paper strength withthe addition of 2.0% EFA-C.

FIG. 17 shows porosity of sheets made with and without EFA-C.

FIG. 18 shows the densification of paper with the addition of 2.0%EFA-C.

FIG. 19 shows a SEM image at 800× of a 40 lb paper sheet without EFA.

FIG. 20 shows an SEM image at 800× of a 40 lb sheet made with 1% EFA-Cadded before the refining step.

FIG. 21 shows Fourier Transform Infrared Reflectance Spectra of paperwith and without EFA.

FIG. 22 shows Near Infrared Correlation Spectrum of paper.

FIG. 23 is a digital printout of a Scanning Electron Micrograph (SEM)images of paper enhanced with EFA and paper without EFA.

FIG. 24 shows a black and white digital printout of an infrared chemicalimage taken of EFA paper.

FIG. 25 is a plot of NIR response and amount of EFA added, for a paperevaluation.

FIG. 26 is a digital printout of a TEM image of an SBF sample, aftercellulase-gold imaging.

FIG. 27 is a digital printout of a TEM of an EFA sample aftercellulase-gold imaging.

FIG. 28 shows the results of a study to evaluate the effect of EFA onfat and moisture content of fried mushrooms.

FIG. 29 shows the results of a study to evaluate the effect of EFA onfat and moisture content of fried zucchini.

DETAILED DESCRIPTION I. General Comments

The disclosure provides a method for processing fiber obtained fromgrains, such as corn, oat, wheat, soy and rice to obtain an enhancedfiber additive. The enhanced fiber additive is suitable for a variety ofuses, including but not limited to, use as a paper additive or as a foodadditive.

As used herein the term “Seed Based Fiber” or “SBF” refers to a non-woodfiber obtained from plants. Seed Based Fiber includes a variety ofpolymers, including cellulose, hemicellulose and lignin. “Cellulose” isa linear polymer of glucose that forms a “backbone” structure of thefiber. Hydrogen bonding between cellulose polymers confers high strengthto cellulose fibers. “Hemicellulose” refers to a class of polymers ofsugars including the six-carbon sugars mannose, galactose, glucose, and4-O-methyl-D-glucuronic acid and the five-carbon sugars xylose andarabinose. Hemicellulose polymers are essentially linear, except forsingle-sugar side chains and acetyl substituents. Hemicellulose polymersare more soluble and labile than cellulose and can be solubilized fromplant cell walls using alkali, such as sodium hydroxide. “Holocellulose”is a term that refers to the total cellulose and hemicellulose contentof fiber. “Lignin” is a complex polymer of phenoxypropanol units thathas an amorphous, three-dimensional structure. Lignin is an adhesive orbinder that holds the fibers together.

By way of example, a typical corn kernel contains (by wt. %) about39-40% hemicellulose (high hemicellulose content, good supplement forcommercial pulp); 11-30% cellulose (low cellulose content, not good forpaper); 3-6% lignin (low, good); <1% ash (low, good); 22-23% starch;3-4% fat; and 10-12% protein.

II. Preparing the Enhanced Fiber Additive (EFA)

II. A. Process Steps

The disclosure provides a method of processing seed based fiber material(SBF) to form an enhanced fiber additive (EFA). The process includestreating the SBF with an acid (“acid treatment step”) to form an acidtreated fiber or modified seed based fiber material. (By “modified” inthis context it is meant that the SBF is no longer in its untreatedform.) The acid treated fiber can be washed and used as an enhancedfiber additive. In preferred processing, the acid treated fiber istreated with a modifying agent (“a surface modification step”) to form amodified fiber. The modified fiber can then be washed and be used as apreferred enhanced fiber additive (EFA). A flow chart of the preferredprocess and some selected variations is shown in FIG. 1. (Optionally,and preferably the SBF can be washed or otherwise treated prior to theacid treatment step.) Herein the term SBF is generally mount to refer tothe fiber material prior to acid treatment, without regard to whether ithas been previously washed or otherwise treated.

II. A. 1. Acid Treatment

In the acid treatment step, SBF is treated with an acid formodification. The modification is observed to soften and loosen thefibers. In the acid treatment step, the SBF is mixed with a dilute acidsolution to form an acid slurry. The acid slurry is allowed to react fora time sufficient to soften and loosen the fibers. Preferably, thereaction is performed at an elevated temperature; i.e., a temperatureabove 80° C., typically at 100° C. to 140° C.

The term “dilute acid solution” refers to a solution in which a smallamount of acid is combined with a large volume of water. The amount ofacid combined with the water can vary depending upon the strength of theacid, the fiber being treated and the desired properties of the enhancedfiber additive. The amount of acid can be calculated based on the weightpercent of the SBF dry weight. The dilute acid solution can be preparedby combining either a strong acid or a weak acid with water. Generally,a dilute acid solution prepared using a weak acid tends to contain alarger molar amount of weak acid than a dilute acid solution preparedusing a strong acid. Typical useable dilute acid solutions arehydrochloric acid, sulfuric acid, acetic acid, perchloric acid andphosphoric acid compositions. Generally, the acid in the dilute acidsolution is included in the amount of about 0.001% to 5% by weight ofthe dry SBF (e.g., about 0.001 to 5 grams of acid is used for every 100grams dry weight of fiber), more preferably about 1% to about 4% byweight of the dry SBF, most preferably about 2% to about 3% by weight ofthe dry SBF. Preferably, the dilute acid solution is combined with theSBF in the ratio of 10:1, more preferably about 6:1, most preferablyabout 3:1.

Preferably the dilute acid solution has a pH below 5, typically withinthe range of about 0.5 to about 3, preferably about 1 to about 3, andmost preferably about 1 to about 2.

The acid treatment step is preferably performed at an elevatedtemperature (above 21° C. typically greater than 80° C.) and over rangeof pressures from atmospheric to 500 psi, typically 10 psi to 30 psi, tofacilitate penetration of the acid into the fibers and to decrease theamount of time necessary for the reaction to be completed. If thetemperature of the reaction is too high, there can be an undesirabledecrease in yield. Therefore, the reaction is preferably performed at atemperature within the range of about 100° C. to about 140° C., morepreferably about 110° C. to about 130° C., most preferably about 115° C.to about 120° C. Preferably the acid treatment step is performed in asealed pressure vessel capable of operating at temperatures greater than100° C. Examples of suitable pressure vessels include a circulationreactor (e.g., Digester from M/K Systems located in Danvers, Mass.) or ajacketed mixing reactor (e.g., Pandia digester from Beloit Corporationlocated in Nashua, N.H.). Typical pressures within the reactor will be10-50 psi. The reactors need not be purged of air.

After the desired temperature is obtained, the reaction is allowed tocontinue for a suitable amount of time, typically for a time sufficientto observe a significant softening and loosening of the fibers.Generally, the acid treatment reaction is carried out for less than 2.5hours, for example about 0.5 to about 2 hours will typically suffice.Typical preferred treatments will be about 1 to about 2 hours, forexample about 1 to about 1.25 hours. After the reaction has continuedfor the desired amount of time, the reactor is cooled to roomtemperature and is vented to atmospheric pressure. Alternately, the hotspent acid solution can be blown out through a condenser under pressureand the solid contents cooled with cold water. The acid treated fiber isthen removed from the reaction vessel.

The acid treated fiber can be washed to remove the spent acid solution.As used herein, “spent acid solution” refers to the dilute acid solutionafter the acid treatment step. The spent acid solution typicallycontains extracted lignin, starch, residual chemicals and otherimpurities not found in the dilute acid solution. Preferably, the acidtreated fiber is washed with water. More preferably, if the acid treatedfiber is to be used as an enhanced fiber additive, the washing step isperformed until the filtrate has a neutral pH (e.g., a pH between about6.0 and 8.0, preferably about 7.0). Typically, a filtrate having aneutral pH can be obtained by exchanging the spent acid solution with 3to 4 volumes of water. The washed acid treated fiber can then be used asan enhanced fiber additive. Optionally, the washed acid treated fibercan be dried.

In preferred processing, the acid treated fiber is washed and furthermodified in a surface modification step. When the acid treated fiber isto be further modified in a surface modification step, it is preferablethat residual acid from the acid treatment step remain with the acidtreated fiber to help maintain an acidic pH during the surfacemodification step. Thus, when the acid treated fiber is to be furthermodified in a surface modification step, the wash preferably removes amajority of any extracted lignin, starch and other particulate matterbut leaves some of the spent acid solution behind. This can typically beaccomplished by exchanging the acid solution with about 1 to 2 volumesof water. It is particularly desirable that residual acid from the acidtreatment step remains with the acid treated fiber when the surfacemodification process includes a mild acid chlorite treatment.

II. A. 2. Surface Modification

The acid treated fiber is preferably treated using one or more surfacemodification steps. A purpose of the surface modification steps is toimprove the brightness of the resulting enhanced fiber additive (EFA)and to improve the hydrophilicity of the EFA. An example of a surfacemodification step is a bleaching step. Although the SBF can be treatedin a surface modification step without a prior acid treatment step, itis preferred that the surface modification step is performed after theSBF has undergone an acid treatment step.

In the surface modification step, the acid treated fiber is contactedwith a modifying agent to form the preferred enhanced fiber additive. Asused herein, “modifying agent” refers to a composition or solution thatis capable of altering the hydrophobicity, hydrophilicity, and/orbrightness of the fiber. A modifying agent preferably increases thehydrophilicity (or decreases the hydrophobicity) of the fiber, forexample, by adding hydrophilic groups or removing hydrophobic groupsfrom the fiber or by altering the surface area of the fiber such thatmore hydrophilic groups (or less hydrophobic groups) are exposed. Thesurface modification agent may also increase the brightness of thefiber, for example, by removing lignin. An example of a surfacemodification agent is a bleaching agent. Bleaching agents used in thewood pulping industry can be used. A mild acid chlorite solution is apreferred bleaching agent. Peroxide (typically hydrogen peroxide) isanother useable bleaching agent. Acid treated fiber can be treated usinga mild acid chlorite solution; a peroxide solution; or, a combination ofboth. The use of an acid chlorite solution in combination with aperoxide solution (in separate steps) as bleaching agents is preferred.The brightness and hydrophilicity of the fibers is typically enhancedwhen both treatments are used.

During a typical acid chlorite treatment, acid treated fiber is combinedwith an acid chlorite solution and heated. As used herein, the term“acid chlorite solution” refers to a solution that includes a chloritesalt, a strong or weak acid, and, optionally, an aqueous carrier.Preferably, the acid chlorite solution has a pH below 5, typicallywithin the range of about 2 to about 5, preferably about 2 to about 4,most preferably about 2.5 to about 3.

The acid chlorite solution is combined with acid treated fiber to form afiber slurry. Water would typically be added to the acid chloritesolution such that the resulting fiber slurry includes about 1 wt % toabout 20 wt % solids, more preferably about 5 wt % to about 10 wt %solids. Typically, the slurry includes about 1% to about 5% by weightchlorite, more preferably about 1% to about 3% by weight, mostpreferably about 1% to about 2% by weight. These weight percentages arerelative to the weight of dry fiber. For example, the slurry can includeabout 1 to 2 grams of chlorite for each 100 grams of fiber (dry weight).

Although the modification step can be performed at room temperature, itis preferably performed at an elevated temperature (>21° C.) to increasethe reaction rate. An undesirable decrease in yield may be observed, ifthe temperature is too high.

Typically, the bleaching step is performed at a temperature within therange of about 50° C. to about 80° C., more preferably about 55° C. toabout 75° C., most preferably about 65° C. to about 75° C. The reactionis typically conducted in a sealed container, under an air atmosphere,with intermittent mixing of contents. The reaction is performed forabout 0.5 hours to about 2 hours, more preferably about 1 hour to about2 hours, most preferably about 1 hour to about 1.5 hours.

After the acid chlorite treatment is completed, the modified fiber canbe washed with water to remove extracted materials and excess chemicalsand can then be used without further treatment as an enhanced fiberadditive (EFA).

The modification step may be selected to include a peroxide treatmentstep. Preferably, if conducted, the peroxide is hydrogen peroxide and iscombined with the fiber in amount of about 1% to about 10% by weight ofdry fiber, more preferably about 2% to about 7% by weight, mostpreferably about 3% to about 6% by weight. Preferably, the peroxide isincluded in a solution that includes peroxide and an aqueous solventsuch as water. Typically, the peroxide solution has a pH of at least 9,for example between 9 and 11.5, preferably between about 9.5 and 11,most preferably between about 10 and about 10.5. Preferably the peroxideis prepared as a mild alkaline solution by adding a base to thebleaching solution to obtain the desired pH.

As with the acid-chlorite treatment, the peroxide treatment can beperformed at room temperature. However, it is again desirable to carryout the reaction at an elevated temperature (>21° C.) to increase thereaction rate and reduce the reaction time. However, the temperatureshould not be too high or the reaction carried out for too long, or theyield may be undesirably decreased. The peroxide treatment step istypically conducted at a temperature of about 50° C. to 80° C., often55° C. to 75° C., preferably about 55° C. to about 65° C.; and for about0.5 to about 2 hours, typically 1 to 2 hours, preferably about 1 toabout 1.5 hours. After the peroxide treatment, the fibers are typicallywashed with water to a pH of about 7.0 to remove excess chemicals andresidual extractives and can be used as an enhanced fiber additive(EFA).

If both the acid chlorite and peroxide treatments are used for surfacemodification, the acid chlorite treatment is preferably performed priorto the peroxide treatment. This is to minimize pH adjustment.

II. A. 3. Additional Process Steps

The enhanced fiber additive (EFA), prepared as described above, can bedried and ground to form a powder. Preferably the EFA is dried at anelevated temperature to decrease drying time. However, if thetemperature is too high, brightness may be reduced. Generally, theprocessed EFA is dried by exposing the fiber to a temperature of atleast 35° C., typically between 40° C. and 70° C., preferably 45° C.-65°C., most preferably about 55° C. to 60° C. for up to 8 hours, or untilthe moisture content of the fiber is less than 6 wt %. The dried EFA canbe ground to any suitable size, depending on the intended use. Forexample, the fiber can be ground to 100-mesh (U.S. Standard) size toprovide a starch-like powder additive. (By ground to 100 mesh it ismeant that the material is ground, and that fraction which passesthrough a 100 mesh U.S. Standard screen is used.) A Retsch mill or anyother type of disintegrator can be used. Care should be taken not tochar or burn the fiber during disintegration.

II. B. Materials Used in Processing

II. B. 1. Acid Treatment Step

Either a strong or weak acid can be used in the acid treatment step.Examples of suitable strong acids include hydrochloric acid, nitric acidand sulfuric acid. Acetic acid (CH₃COOH), citric acid, sulfurous acidand carbonic acid (H₂CO₃) are examples of suitable weak acids.Preferably, the acid is a strong acid. Most preferably, the acid issulfuric acid or hydrochloric acid.

II. B. 2. Surface Treatment Step

Bleaching agents are known. “Handbook for Pulp & Paper Technologists,”by G. A. Smook, published by TAPPI (1989) provides a discussion of avariety of bleaching protocols which are useful and is herebyincorporated by reference herein. Examples of suitable bleachingtreatments include reacting fibers with elemental chlorine in acidicmedium; alkaline extraction of reaction products with sodium hydroxide;reacting fibers with hypochlorite in alkaline solution; reacting fiberswith chlorine dioxide in acidic medium; reacting fibers with peroxidesin alkaline medium; reacting fibers with elemental oxygen at highpressure in alkaline medium; and reacting fibers with ozone.

A mild acid chlorite solution is a preferred modifying agent. Examplesof suitable chlorites include sodium chlorite, calcium chlorite,magnesium chlorite and potassium chlorite. A preferred chlorite issodium chlorite. Preferably, the chlorite is combined with a strong acidsuch as hydrochloric acid or sulfuric acid and an aqueous carrier suchas water. For example, the acid chlorite solution include a 1:1 molarratio of sodium chlorite and hydrochloric acid. Alternately, the acidchlorite solution can include a 2:1 ratio of potassium chlorite andsulfuric acid.

Another preferred modifying agent includes peroxide. Hydrogen peroxideis an example of a suitable peroxide. Preferably, the peroxide isprepared as a mild alkaline solution by combining the peroxide with anaqueous carrier (water) and a basic material. Sodium hydroxide andpotassium hydroxide are examples of suitable basic materials.

Optionally, a chelating agent can be included in the peroxide solution.Chelating agents are known. An example of a suitable chelating agent issodium metasilicate. The chelating agent will bind various metal ions inthe system.

III. Selected Properties of the Enhanced Fiber Additive (EFA)

The process provides a modified, processed fiber, referred to as anenhanced fiber additive (EFA). If the EFA has not been modified bybleaching, it typically has a brightness of the same color as thestarting material. The preferred EFA is generally white to light tan incolor and typically has a brightness of at least about 50 ISO,preferably at least about 70 ISO, and most preferably is the result oflightening to at least about 80 ISO. The brightness or whiteness offiber can be measured by its ability to reflect blue light in comparisonto a known standard of magnesium oxide at a specific detectionwavelength and reflectance angle (TAPPI Test Methods T 452 om-87).

The EFA can be characterized by significant water and oil holdingcapacity as measured by a modification of AACC (American Association ofCereal Chemists) Method 56-20. The method is described in Example 7.Typically, the EFA has a water holding capacity of at least 200 wt. %,generally at least about 300 wt. %, and, when prepared in accord withpreferred processing described herein, about 500 wt. %. The oil holdingcapacity of the EFA typically is at least 150 wt. %, generally at least200 wt. %, and, when prepared in accord with preferred processingdescribed herein, about 300%.

The EFA also exhibits viscosity building characteristics in aqueoussolutions under high shear or homogenizing conditions. A homogenizedaqueous solution which includes 1.5 wt % EFA typically exhibits aviscosity of at least 10 cP using a Brookfield Corporation viscometer,generally at least about 100 cP, and, when prepared with EFA made inaccord with preferred processing herein, has a viscosity of at leastabout 400 cP.

The EFA, when prepared from corn, typically is at least about 70% to100% by weight carbohydrate (including cellulose and hemicellulose),more typically about 80% to about 95% by weight, and in some instancesabout 85% to about 95% by weight. The majority of the carbohydratefraction, about 75% by weight to about 95% by weight is insolubledietary fiber. More typically, when prepared from corn the EFA is about85% to about 90% by weight insoluble dietary fiber.

EFA derived from oats is typically at least 80% to 100% by wt.carbohydrate (including hemicellulose and cellulose), more typically 80%to 90%, by wt.; and, in some instances, about 85% to 90% by wt. EFAderived from soy is typically 70% to 100% by wt. carbohydrate (includingcellulose and hemicellulose), more typically about 80% to 95% by wt.;and, in some instances, about 80% to 85% by wt.

The desirable characteristics of the enhanced fiber additive arebelieved to result from chemical modifications leading to changes in theholocellulose, hemicellulose and cellulose nature of the material. Thisis described in section VIII below. In general, the processing isobserved to lead to a greater cellulose character, versus hemicellulosecharacter, in the fiber material (when comparing the fiber materialbefore and after processing). In addition, many of the observationsrelating to the structure, color, and exposure of the cellulosecharacter are believed to relate to lignin modification at least at thesurface, as a result of the physical and chemical modifications.

When examined using a Scanning Electron Microscope, the structure of theground enhanced fiber additive (EFA) tends to have an increased surfacearea when compared to unprocessed fiber, such as ground corn fiber(SBF-C). Whereas the SBF-C typically has a structured, jagged androck-like appearance, the EFA tends to have a lighter feathery, bloomedappearance. The increased surface is believed to be responsible, inpart, for many of the desirable properties of the EFA.

IV. Uses for the EFA

IV. A. General Comments on Use

The EFA can be used to modify adhesive or rheological properties of avariety of commercial products. For example, the EFA can be used inpaper coating formulations and paints. The EFA can also be used in foodformulations. Additionally, the EFA is suitable for enhancing strengthproperties of paper.

IV. B. Papermaking

In the paper industry, additives are frequently used to modify theproperties of paper. For example wet end starches are added for internalsizing; and, inorganic fillers (e.g., calcium carbonate, titaniumdioxide, and clays) are added for optical enhancement properties and asfiber replacement materials. Other synthetic strength enhancingadditives are also known.

The EFA is also suitable for use in papermaking, preferably as a fiberreplacement material. The EFA is natural, low in ash content and lightin weight. In contrast to inorganic fillers, the EFA can be used in amanner that does not significantly add to the weight of the paper sheet.Indeed, EFA made as described herein has been found to maintain orincrease paper strength properties in applications wherein the basisweight of the paper is decreased by more than 10%, for example up to33%. The ability of the EFA to increase paper strength in applicationswithout concomitant increase in basis weight is attractive for both thepaper manufacturing facility and the paper customer. The papermanufacturer can benefit by application to achieve lower material andoperational costs, while the paper customer can benefit from applicationto achieve lower shipping and mailing costs. In particular, newsprintand LWC (Light Weight Coated) papers could well benefit from the reducedpaper basis weight due to use of the EFA.

For some papermaking applications there is less concern with wood fiberreduction, and more concern with paper strength enhancement. The EFA hasbeen found to enhance paper strength properties even at catalyticaddition levels. As used herein, the term “catalytic addition levels”means the EFA is added to the paper in a minor amount, typically at alevel of less than 10 weight %, usually at a concentration of 0.1 weight% to 10 weight %, based on the papermaking pulp content; more generallyabout 0.5 weight % to 3.0 weight %, and preferably, about 0.5 weight %to 2.0 weight %. Markets that benefit from strength enhancement includeliquid packaging, bleached board, fine paper, linerboard, and corrugatedboard.

Additionally, EFA is an environmentally friendly papermaking additive.Wood fiber use can be reduced by, for example, 5% up to 33% (weight %)while using only catalytic amounts of EFA. The reduction in wood fiberconsumption not only preserves the wood fiber supply, but alsosubsequently reduces the amount of pulping and/or bleaching chemicals,sewer B.O.D. (Biological Oxygen Demand), energy consumption (e.g.,electrical and/or fossil fuel power), and productshipping/transportation costs.

IV. B. 1. The Papermaking Process

Paper is basically formed from a web of pulp fibers. Pulp is a fibrousraw material for papermaking and is usually of vegetable origin.However, animal, mineral or synthetic fibers may be included. The pulpused in papermaking is most commonly derived from wood sources. Non-woodsources such as cereal straws or such materials as linen/flax; hemp; andsynthetic fibers (e.g., polyethylene fibers) are usable of coarsemixtures can be used. In the paper product, the result of thesematerials is referenced herein as “paper fiber”. Typically such non-woodsources are used in significantly lower quantities. Pulp can also bederived from secondary or recycled fibers.

Paper is typically formed from an aqueous slurry of pulp or otherfibers, which is filtered through a wire or screen and dried. The papermanufacturer typically obtains pulp from raw materials such as woodchips, boards, straw, jute, clothe or recycled paper by wetting andbeating the raw material to separate the paper fibers and to form afiber slurry. The fiber slurry is then refined, in a refining machine,to make the surface of the fibers more rough.

Once a pulp is obtained, paper can be formed by hand or by machine. Thesame basic steps are involved for either hand- or machine-made paper:(1) forming; applying the pulp slurry to a screen; (2) draining;allowing water to drain by means of a force such as gravity or apressure difference developed by a water column; (3) pressing; furtherdewatering by squeezing water from the sheet; and (4) drying; air dryingor drying the sheet over a hot surface. Importantly, the pulp should beapplied to the screen at a low consistency (e.g., about 0.1% to about1.0% solids) to provide an even distribution of fibers and paperuniformity (G. A. Smook; 2^(nd) Edition Handbook for Pulp and PaperTechnologists; Angus Wilde Publications Inc. 1994).

The pulp making process can be chemical, mechanical, orchemi-mechanical—depending on the desired amount of lignin removal.Pulps produced using chemical means are usually stronger and easilybleached to increase brightness. Mechanical pulps, on the other hand,tend to retain more lignin. Mechanical pulps thus tend to be weaker andmore difficult to bleach. Chemi-mechanical pulps generally have strengthproperties somewhat in between of chemical and mechanical pulps.Different grades of paper are made with different types of pulp. Forexample, newsprint grades typically use mechanical pulps. High qualitywriting and printing grade papers typically use bleached chemical pulps.

As indicated above, chemicals are typically added during pulping toremove lignin. However, the chemicals also tend to remove hemicellulosefrom fibers as well. It is generally desirable to retain somehemicellulose content because hemicellulose is a natural binding agentwhich provides additional tensile and bursting strength to paper pulp.Therefore, it may be desirable to replace the lost hemicellulose with ahemicellulose containing additive, such as EFA (Enhanced Fiber Additive)made in accord with process described herein.

IV. B. 2. Use of the EFA in Papermaking—General Comments

Preferably a papermaking fiber additive is low in fats, proteins, ligninand ash but high in holocellulose and inclusive of hemicellulose.Hemicellulose is hydrophilic and thus promotes hydrogen bonding betweenthe individual paper fibers. Thus, hemicellulose functions as a binderand improves paper strength. Because lignin is hydrophobic and adds ayellowish color to the resulting paper, it is generally desirable tominimize the amount of lignin in a paper additive. Lignin also acts as aglue, which holds the individual fibers together. In contrast, it ispreferred that the individual fibers are easily dispersible.

Although other fibers (with higher lignin content) can be used as astrength additive, corn fiber is of particular interest as a paperadditive because corn fiber has an adequate hemicellulose content andrelatively low lignin and ash contents. For example, whereas corn fiberhas about 3-6% lignin, soft wood contains about 25-31% lignin andhardwood contains about 16-24% lignin.

Processing according to the present invention, as will be apparent fromthe discussion in section VIII below can be conducted to lead to amodified or enhanced fiber additive which has particularly desirablechange of characteristic with respect to holocellulose character,hemicellulose character, and cellulose character, versus the SBF rawmaterial from which it is made. The relatively high cellulose charactermeans that the fibrous material will behave in a manner similar to woodfibers, in dispersability and alignment, within the paper. The definedhemicellulose character in part means that desirable strengthenhancement will occur. The overall total holocellulose content, meansthat other undesirable effects are reduced to an acceptable level. Inaddition, it is believed that the modifications of surfacecharacteristics and lignin characteristics also facilitate the operationof the material as a paper additive.

IV. B. 3. Processing

The EFA can be added to papermaking pulp slurry prior to or during therefining or beating stage of the paper making process (FIG. 8B).Preferably, the EFA is refined along with the paper making pulp slurryto enhance mixing and contact between the EFA and the paper making pulpfibers. The EFA is preferably added in an amount that is sufficient toenhance the properties of the resultant paper, but not so high that itundesirably inhibits drainage of the papermaking pulp or adverselyaffects operation of equipment. Preferably, the EFA is added to thepapermaking pulp at a concentration of about 0.1 weight % to about 10weight % based on the papermaking pulp content, more preferably about0.5 weight % to about 3.0 weight %, most preferably about 0.5 weight %to about 2.0 weight %.

Optionally in addition to the EFA, a cationic starch can be added to thepaper slurry system to provide flocculation for the fiber, aid indrainage of the water, and retain fibers and filler material. Cationicstarches are produced by a chemical reaction of starch with reagentscontaining amino, imino, ammonium, sulfonium, or phosphonium groups, allof which can carry a positive charge. Currently, the commerciallysignificant derivatives are the tertiary amino and quaternary ammoniumstarch ethers. A key factor in their usefulness is an affinity fornegatively charged substrates (O. B. Wurzburg; Modified Starches:Properties and Uses; CRC Press Inc., 1986).

The EFA provides for the option of reduction in papermaking pulp, forexample, up to 33%, while maintaining the burst and tensile strengthproperties of the paper. Additionally, the EFA increases wet strengthand runability during the papermaking process such that machine speedscan be increased and web breaks for lightweight paper grades arereduced.

Referring to FIG. 8A, Lou Calder paper machine operation is shown. Sucha machine could be used to achieve production with a machine speed of 6fpm to 150 fpm, to produce 75 lbs per hour to 200 lbs per hour of paperhaving a basis weight of 18 lbs to 400 lbs.

At reference No. 1, a Hollander feeder is depicted. The machine chest isindicated at 2, the beater chest at 3 and the back chest at 4. The traywater box is indicated at 5, with ph control at 6, the table rolls at 7,the dandy roll at 8, the first press at 9, the second press at 10, thesize press at 11, the first dryer at 12, the second dryer at 13 and thetakeup roll at 14. The suction couch is indicated at 15.

Such equipment is standard papermaking equipment, and useable inpapermaking processes according to the descriptions herein.

IV. B. 4. Product

This disclosure also provides a paper product which includes the EFA.The EFA may be used to improve many properties of paper, for example,the internal bond strength of the paper such as burst, Scott bond, andtensile; and bulking/packaging properties such as bulk density. All ofthese paper properties can be measured using published TAPPI testmethods.

The EFA is suitable for use in a variety of paper materials. Papermaterials are classified as paper (newsprint, stationary, tissue, bags,towels, napkins, etc.) or paperboard (linerboard, corrugated media,tubes, drums, milk cartons, recycled board used in shoe and cerealboxes, roofing felt, fiberboard, etc.). The industry typically dividespaper into broad categories based on the types of fibers used in thepaper and the weight of the paper. The EFA is suitable for use in allclasses of papers. However, it will typically be used to enhance theproperties of high-grade papers such as bond papers, fine papers, andpaperboard such as linerboard or corrugating medium.

Bond papers are a broad category of high quality printing or writingpapers. They are made from bleached chemical pulps and cotton fibers andmay be watermarked. Fine papers are intended for writing, typing andprinting purposes. They may be white or colored, are made from bleachedKraft or sulfite softwood pulps, and may contain hardwood pulps forsmoothness and opacity. Linerboard is an unbleached Kraft softwood sheetof southern pine or Douglas fir made in various weights. Frequently,linerboard is a two-ply sheet. The compression strength and burststrength of the linerboard is important. Corrugating medium is made fromunbleached, semi-chemical pulp. It is formed into a wavy structure andsandwiched between plies of linerboard to form a corrugated structure.Corrugating medium is usually used to make boxes.

C.

IV. B. 5. Additional Observations

In general, for material to have good property as an additive forpapermaking, in the manner of the EFA use as an additive, the materialshould provide the following:

-   -   (A) The good hydrophilicity of hemicellulose;    -   (B) A cellulose-like fiber property; and    -   (C) A fiber structure capable of forming bridging microfibrils        in the paper.

The hemicellulose hydrophilicity helps with the dispersion capabilitiesof the materials, as well as hydrogen bonding to the cellulose materialin the pulp. Cellulose-like fiber properties provide for goodintermingling with the other cellulose fibers in the pulp. Anappropriate microfiber structure allows for the formation ofmicrofibrils which can add to overall strength of the paper by forming abridging network between pulp (cellulose) fibers.

As indicated above and through the following experiments, enhanced fiberadditive (EFA) made according to the present invention, provides such amaterial. In general, as a result of the modification: (a) the percentcellulose character in the overall fiber material is typically higherthan it was prior to treatment; (b) the ratio of cellulose character tohemicellulose character is typically increased relative to the startingfiber; and (c) the holocellulose character is typically increased. Thematerial has a distinctive, observable, micro structure, and providesthe formation of a microfibril structure in the paper product, asindicated by the examples below and depicted in the comparisons of FIGS.19 and 20. The observable cellulose-like structure allows the materialsto align with cellulose pulp materials, as characterized below inconnection with the Examples.

IV. C. Use of EFA as a Food Additive

Dietary fiber is important for the digestive process and has a role inthe prevention of diseases such as colon cancer. Dietary fiber is alsothought to reduce serum cholesterol levels, which is important in theprevention of heart disease. “Dietary fiber” includes soluble andinsoluble components of plant cell walls that are not digested byendogenous (non-bacterial) enzymes of a human digestive tract. Dietaryfiber is not absorbed in the small intestine and thus enters the largeintestine (colon). “Insoluble fiber” includes oligo- and polysaccharidessuch as cellulose and hemicellulose. “Soluble fiber” is used to denotefiber that is at least 50% soluble according to the method described byL. Prosky et al., J. Assoc. Off. Anal. Chem., 71, 1017-1023 (1988).Examples of soluble fiber include pectin, beta-glucans (smallcellulose-type branched glucose polymers), and gums such as xanthan gum.Uses of fiber additives in foods are reported as dietary fiber under theNutrition Labeling and Education Act (NLEA) of 1990.

It is common for food manufacturers to use a combination of insolubleand soluble fiber in food formulation. The insoluble fiber products areused largely for fortification, and the soluble fiber products forfunctionality. Functionality includes appearance, viscosity buildingcapability, water holding capacity, and oil holding capacity.

Because the EFA has both a significant water holding capacity (i.e.,hydrophilic character) and a significant oil holding capacity (i.e.,lipophilic character), not only can it be used as an emulsifier,viscosity builder or for similar reasons, but also it can be enhanced orfortified with other materials, and used as part of the deliveryvehicle, for example to deliver a nutraceutical. Thus, it can befortified with various nutrients, dietary supplements, etc., prior toincorporation into food products or prior to direct ingestion.

The EFA is suitable for use as a dietary fiber supplement. Unlike manycommercially available fiber additives, the EFA provides bothfortification and functionality. More specifically texture, thickening,and mouthfeel are improved due to its absorbency.

Typically, the EFA will be used in an amount of at least about 0.5%, forexample, about 1% by wt. of the total contents of a food preparation mixbefore processing, whether solid or liquid, from which the food isprepared. In baked goods, at least 0.5%, for example, 1% or more,typically at least 3% by wt. on the basis of flour components, isuseable.

IV. C. 1. Processing

EFA can be included in a food formulation or nutritional supplement. Itcan be used in any current food formulation that incorporates insolublefiber, and, due to its viscosity-building properties, may replace, inwhole or in part, soluble fiber products in current food formulations.

IV. C. 2. Food Products

This disclosure also provides a food product that includes EFA. Becauseof its viscosity building characteristics, EFA is suitable for use innutrition beverages to impart a thick, creamy mouthfeel, to help suspendfine solids like cocoa powder and minerals, and to help stabilize theemulsion. It can also be used as a clouding agent, in juices. Due to itsviscosity building characteristic, EFA is also suitable for use toachieve a desirable texture and cling in salad dressing or similardressings, sauces, and fillings.

The water holding capacity of the EFA makes it suitable for use as anadditive to prevent staling in baked goods such as bread and bagels.Advantageously, EFA is suitable for use in baked goods and bakery itemsthat are generally consumed for fiber fortification. Furthermore, thewater holding capacity of EFA makes it suitable as a component toprovide freeze/thaw stability in frozen foods, and to increase cookingyield in meats like ground beef.

In general, for flour containing food products, the EFA will typicallybe useable in any acceptable amount. For example, at least 0.5% or moreby wt. of flour ingredient. In food preparations generally, includingbeverages and solid food mixes, the EFA will typically be useable in anyacceptable amounts, for example, at least 0.5% by wt. based on totalingredient weight before processing such as any cooking.

IV. D. Other Uses of EFA

The EFA can also be used in adhesive formulations to improve bindingstrength and water holding characteristics. The EFA can be used toimprove rheological properties of paint formulations withoutcontributing to VOC's (Volatile Organic Compounds). Paper coatingformulations often contain compounds (e.g., CMC (Carboxymethylcellulose)to modify the water holding ability of the coating color. Due to itshigh water holding capacity, EFA can be beneficial in paper coatingapplications.

V. Examples Example 1 Acid Treatment

EFA can be prepared using corn fiber, for example, SBF from corn wetmilling operations. Corn fiber (SBF-C) was obtained from Cargill CornMilling, Cedar Rapids, Iowa. The corn fiber (SBF-C) was washed on a70-mesh screen using a fine spray of water to remove fiber fines, freestarch and protein. The moisture content of the resulting washed fiberwas determined to be 50%. Approximately 1200 grams (600 grams on drybasis) of the fiber was then loaded in the screened basket (having a100-mesh screened bottom) of an M/K digester and inserted in thepressure vessel.

A dilute acid solution containing 2% sulfuric acid (based on fiber dryweight) was combined with the SBF at a ratio of dilute acid solution toSBF of 10:1 (weight basis). The dilute acid solution contained 12 gramsof 100% sulfuric acid (or 12.5 grams of the acid purchased at 96%concentration) and 5387.5 grams of water. The amount of sulfuric acidand water in the dilute acid solution was determined as shown below:

-   Total weight of the dilute acid solution: 600 g×10=6000 g-   Amount of water needed: 6000−600 g (from wet fiber)−12.5 g of    H₂SO₄=5387.5 g of water

The dilute acid solution was slowly added to the corn fiber in thedigester and the circulation pump was turned on. After confirming thatthe dilute acid solution was being circulated in the reactor, thereactor lid was sealed. The reaction temperature was set at 120° C. andtime to reach reaction temperature was set at 45 minutes and then wasset to be maintained for 1 hour. The heater in the reaction vessel wasturned on. The temperature and pressure inside the reactor were recordedas a function of time. After reaching the target temperature of 120° C.,the reaction was continued for 1 hour. After 1 hour, the cooling watersupply to the reactor was turned on to cool the reactor contents. Thespent dilute acid solution was drained from the reactor by opening adrain valve on the reactor. The fiber content in the reactor basket wascarefully removed and washed using two washing batches of 6 liters ofwater each. The washing was continued further until the wash water had aneutral pH (e.g., between 6.0 and 8.0, typically about 7.0).

Example 2 First Surface Modification: Acid Chlorite Treatment

The acid treated fiber from Example 1 was then treated in a surfacemodification step. The acid treated fiber was combined with an acidchlorite solution to form a fiber slurry that included 10% fiber and 90%acid chlorite solution. The acid chlorite solution included 1.5% byweight (based on dry fiber) of sodium chlorite and 0.6% by weight (ofdry fiber) of hydrochloric acid. The reaction was carried out in asealed plastic bag at a temperature of 65-75° C. for 1 hour at a pHbetween about 2 and 3. After treatment with the acid chlorite solution,the fiber slurry was diluted with 2 liters of water and filtered in aBuchner type funnel. This step was repeated until the resulting filtratewas clear and at neutral pH (e.g., pH 6.0 to 8.0, preferably about 7.0).

Example 3 Second Surface Modification: Peroxide Treatment

The acid chlorite treated fibers from Example 2 were then treated withan alkaline peroxide solution. The fibers were combined with 3-8% byweight (of the dry fiber) of hydrogen peroxide and 2% by weight (of thedry fiber) sodium hydroxide at a pH between about 10-10.5 and at asolids concentration of 10-20%. Sodium metasilicate was added (3% byweight of dry fiber) as a chelating agent. The peroxide treatment stepwas conducted in a sealed plastic bag at 60-65° C. for 1 hour. After thereaction, the fiber slurry was diluted with 2 liters of water andfiltered in a Buchner funnel. This step was repeated until the resultingfiltrate was clear and at neutral pH. The bleached processed fiber wasdried in an air-circulated oven at a temperature of 35-60° C. and thenground to 100-mesh size (e.g., 150-250 micron) using a Retsch mill.

Example 4 Structure: Scanning Electron Microscope

The structure of ground corn fiber (SBF-C) from the corn wet millingprocess and the structure of the ground enhanced fiber additive (EFA-C)from Example 3 were examined at 100× using a Scanning ElectronMicroscope (SEM). Samples were dried and prepared using standard SEMsample preparation techniques. FIGS. 2 and 3 show the Scanning ElectronMicrographs for ground corn fiber (SBF-C) and enhanced fiber additive(EFA-C), respectively. The ground corn fiber (SBF-C) has a jagged androck-like appearance. The unprocessed fiber is very structured (inbundles) (FIG. 2). The structure of the ground enhanced fiber additiveis substantially different when compared with SBF-C. Whereas the SBF-Chas a jagged and rock-like appearance, the EFA-C has a lighter, morewispy, feathery or bloomed appearance. As a result, the EFA-C has anincreased surface area when compared to the untreated fiber.

Herein, the type of structure observed for EFA under a Scanning ElectronMicroscope (SEM) at 100×, and exemplified in FIG. 3 (by comparison toFIG. 2) will be referred to as a feathery, bloomed structure. It is acharacteristic of typical enhanced fiber additives according to thepresent invention, that when viewed in accord with the experimentcharacterized above, that such an appearance is noted, in at least aportion of the particles. Generally, the appearance is most noted in thelarger particles of the sampling, especially those exhibiting a particledimension in the SEM of 100 micrometers or larger.

Example 5 Composition: Raman Spectra

The Raman scattering spectra of the SBF-C and EFA-C were compared. AFourier transform Raman spectral comparison of the two fibers is shownin FIG. 4. The most prominent difference between the two spectra is inthe disappearance of the bands associated with lignin at 1600 cm⁻¹ and1630 cm⁻¹ (U. P. Agarwal and Sally A. Ralph, Appl. Spectrosc, 51, 1648,1997).

Example 6 Composition: Effect on Lignin Content

The Kappa number and % Klason for the SBF-C and EFA-C were determinedusing the methods described in Tappi Test method T236 cm-85, publishedby Tappi and incorporated herein by reference. The results are shown inTable 1. As can be seen from Table 1, almost 90% of the lignin from theSBF-C was removed by the modification process. This corroborates thedata seen in the FT-Raman reflectance analysis of example 5.

TABLE 1 Comparison of Kappa Number (KN) of SBF-C and EFA-C Calc. %Normalized % Lignin Sample KN Klason % Klason Removed SBF-C 72.7 10.9 100 EFA-C 15.3 2.3 1 89

EFA-C in this Example was prepared in accord with Examples 1, 2 and 3;i.e., with acid, chlorite and peroxide treatment.

Example 7 Chemical and Dietary Fiber analysis

Samples of the EFA-C were submitted to Medallion Labs (Minneapolis,Minn.) for proximate chemical analysis and dietary fiber analysisconsistent with NLEA (Nutritional Labeling and Education Act) methods.Results of the proximate chemical and nutritional analyses of thebleached processed fiber are summarized in Table 2. References to theofficial methods, published by AOAC International, are included in thetable.

TABLE 2 Composition and Properties of EFA-C Percent dry Component solidsbasis (%) Method Reference Total carbohydrates 88.3 Calculated bydifference Total dietary fiber (insoluble) 87.2 AOAC 991.43 Total fat6.39 AOAC 996.06 Moisture 2.5 AOAC 926.08 Protein 2.38 AOAC 968.06 Ash0.44 AOAC 923.03 Oil holding capacity % 300% See below Water capacity %540% See below

The analysis shows that the enhanced fiber additive is largely insolublefiber, or dietary fiber according to NLEA guidelines. This is adesirable component for a fiber food additive.

The percent water holding capacities (WHC) of the fibers were determinedusing a modification of AACC (American Association of Cereal Chemists)Method 56-20. In the water holding capacity test, 1.25 g of fiber wasmixed with an excess of water (12.5 mL) in a pre-weighed 50 mLcentrifuge tube. The pH of the mixture was adjusted to 7.0 and thesample was allowed to hydrate at room temperature with intermittentmixing for 60 minutes. The sample was then centrifuged at 6000×g for 25minutes. Excess water was removed by inverting the tube at a 45-degreeangle for 30 seconds. The percent WHC was determined by dividing thefinal weight of the tube contents by the initial weight of the fibersample and multiplying by 100. The percent WHC is interpreted as themaximum amount of water that 1 gram of fiber will retain under low speedcentrifugation.

The oil holding capacity (OHC) was determined using the same approach asthe water holding capacity, except that the pH was not adjusted and cornoil was substituted for the deionized water.

Example 8 Papermaking: Laboratory Investigation of EFA-C

Papermaking Furnish Preparation: Hardwood and softwood bleached Kraftcommercially available market pulp was received from Georgia Pacific. A50% hardwood and 50% softwood blend was slurred with distilled water to1.2% by weight consistency in a 5-gallon container. 0.5% by weight ofEFA-C (Enhanced Fiber Additive made from Corn Fiber) was added to the1.2% consistency hardwood/softwood papermaking slurry.

Refining: Tappi Method T-200 describes the procedure used for laboratorybeating of pulp using a valley beater. The hardwood/softwood papermakingpulp furnish containing the EFA-C was refined using a valley beater. Thefurnish was refined to 450 mL CSF (Canadian Standard Freeness). Thefreeness of the pulp was determined using the TAPPI test method T-227.Once 450 mL CSF was obtained, the furnish was diluted to 0.3%consistency with distilled water and gently stirred with a Lightningmixer to keep the fibers in the papermaking furnish suspended.

Making Handsheets Paper was made using the following handsheet procedureaccording to TAPPI Test Method T-205. Basis weights of 1.2 gramhandsheets (40 lb sheet or 40 lb/3300 ft² or 60 g/m²) and 1.8 gramhandsheets (60 lb sheet or 60 lb/3300 R² or 90 g/m²) were forcomparison. In some instances, 20 lb/ton of a cationic dent corn starch(Charge +110 from Cargill) was added to the handsheet mold to aid indrainage and retention.

Handsheet Testing: The paper handsheets were submitted to IntegratedPaper Services (IPS, Appleton, Wis.). The paper handsheets wereconditioned and tested in accordance to TAPPI test method T-220 PhysicalTesting of Pulp handsheets. Instruments used: Caliper—Emveco ElectronicMicroguage 200A; Burst—Mullen Burst Test Model “C”; Tear—Elmendorf TearTester; Tensile—SinTech.

Results: Table 3 represents the paper properties from the handsheetevaluation with and without the EFA-C.

TABLE 3 Handsheet Paper Test Results Caliper (mils) Basis Wt (g/m²)Burst Index (kPA m²/g) Tear Index (mN m²/g) Tensile Index (N-M/g)Handsheet No 20 lb/t No 20 lb/t No 20 lb/t No 20 lb/t No 20 lb/t (g)Starch CH + 110 Starch CH + 110 Starch CH + 110 Starch CH + 110 StarchCH + 110 Control 40 lb 20.25 21.00 63.22 64.72 3.38 3.70 12.81 13.0046.96 52.33 Control 60 lb 29.39 29.46 97.75 95.21 3.76 4.20 14.64 13.2551.49 55.34 EFA-C 40 lb 20.00 21.41 66.01 69.42 3.80 4.33 11.60 11.2151.54 58.59 EFA-C 60 lb 28.91 29.59 101.65 102.35 4.05 4.67 13.58 12.3957.78 59.14

The burst strength of paper handsheets with and without EFA-C is shownin FIG. 5. The Figure also demonstrates the enhanced burst strength withthe addition of 20 lb/ton of cationic starch. Note the 60 lb sheetwithout the EFA-C (control) has equivalent burst strength to the 40 lbsheet with 0.5% EFA-C.

The tensile strength exhibited by the paper handsheets with and withoutthe EFA-C is shown in FIG. 6. The Figure also demonstrates the enhancedtensile strength with the addition of 20 lbs/ton of cationic starch.Note the 60 lb sheet without EFA-C (control) has at least equivalenttensile strength to the 40 lb sheet with 0.5% EFA-C.

Conclusion: A 40 lb sheet made in the laboratory with 0.5% EFA-C retainsequivalent burst and tensile strengths as a 60 lb sheet without EFA-C. Acatalytic amount of EFA-C (0.5%) replaced 33% of the Kraft wood fiber ina standard 60 lb sheet without sacrificing burst and tensile strengths.The addition of 20 lb/ton of cationic starch also elevated burst andtensile properties.

Example 9 Papermaking: Laboratory Investigation of EFA-Soy and EFA-Wheat

Papermaking Furnish Preparation: Hardwood and softwood bleached Kraftcommercially available market pulp was received from Georgia Pacific. A50% hardwood and 50% softwood blend was slurried with distilled water to1.2% by weight consistency in a 5-gallon container. 0.5% by weight ofEFA-S (Enhanced Fiber Additive made from Soy Hulls) was added to thehardwood/softwood slurry blend. Another hardwood/softwood blend wasprepared as described above, with 0.5% by weight EFA-W (Enhanced FiberAdditive made from wheat midds).

Refining: Tappi Method T-200 describes the procedure used for laboratorybeating of pulp using a valley beater. The hardwood/softwood papermakingpulp furnish containing the EFA-S and EFA-W were refined using a valleybeater. The furnishes were refined to 450 mL CSF (Canadian StandardFreeness). The freeness of the pulps were determined using the TAPPItest method T-227. Once a 450 mL CSF was obtained, the furnishes werediluted to 0.3% consistency with distilled water and gently stirred witha Lightening mixer to keep the fibers of the papermaking furnish insuspension.

Making Handsheets: Paper was made using the following handsheetprocedure according to TAPPI Test Method T-205. Basis weights of 1.2gram handsheets (40 lb sheet or 40 lb/3300 ft² or 60 g/m²) and 1.8 gramhandsheets (60 lb sheet or 60 lb/3300 ft² or 90 g/m²) were chosen forcomparative reasons. 20 lb/ton of a cationic wet end starch(AltraCharge+130 from Cargill) was added to the handsheet mold to aid indrainage and retention.

Handsheet Testing: The paper handsheets were submitted to IntegratedPaper Services (IPS, Appleton, Wis.) for evaluation. The paperhandsheets were conditioned and tested in accordance to TAPPI testmethod T-220 Physical Testing of Pulp handsheets. Instruments used:Caliper—Emveco Electronic Microguage 200A; Burst—Mullen Burst Test Model“C”; Tear—Elmendorf Tear Tester; Tensile—SinTech.

Results: The results of the handsheet evaluation with and without theEFA-S and EFA-W are recorded in Table 4.

TABLE 4 Handsheet Paper Test Results Target Tensile Basis Wt Basis WtBurst Index Tear Index Index Sample (lb/3300 ft²) (lb/3300 ft²) (kPam2/g) (mN m²/g) (N M/g) Control 40 44.70 3.61 9.86 56.30 Control 6068.06 3.85 11.77 59.12 EFA-S 40 43.72 3.87 11.15 55.32 EFA-S 60 68.084.20 10.89 57.72 EFA-W 40 41.89 3.98 8.60 55.95 EFA-W 60 63.27 4.5410.25 59.61

The burst strength exhibited by the paper handsheets with and withoutthe SFA-S and EFA-W is shown in FIG. 7. Note that the 60-lb controlsheet without EFA-S or EFA-W has equivalent burst strength as a 40-lb.sheet with 0.5% EFA-S or EFA-W.

Conclusion: A 40 lb sheet made in the laboratory with 0.5% EFA-S andEFA-W retains equivalent burst strength as a 60 lb sheet without EFA-Sor EFA-W. No tensile enhancement with EFA-S or EFA-W was measured in thelaboratory as previously seen with the EFA-C.

Example 10 Papermaking: Pilot Paper Machine Investigation of EFA-C

A pilot paper machine trial was performed at Western Michigan Universityin the Paper Science & Engineering Department. Production capabilitieswere as follows: Production rate: 75 lb/hr to 200 lb/hr, Trim basisweight 18 lb/3300 ft² to 400 lb/3300 ft², Machine speeds 6 μm to 150fpm. FIG. 8A shows a schematic of the pilot papermaking plant.

Referring to FIG. 8A, the thick stockflow is indicated at 30, the basisweight control valve at 31, mixing and-addition tanks at 32 and 33, thehead box system at 35, the dandy roll at 36, the couch roll at 37 withthe drainage box at 38, the drain to the sewer line at 39. The equipmentcould be used to obtain a production of about 160 lbs per hour.

Papermaking Furnish Preparation: Hardwood and softwood bleached Kraftcommercially available market pulp was supplied by Western MichiganUniversity. Two different batches of a 60% hardwood and 40% softwoodfurnish were prepared for the study. One batch contained no EFA-C andwas labeled “Control”. The other batch contained 0.5% EFA-C and waslabeled “EFA-C” batch. Each batch was prepared as follows: A 5% byweight consistency of 60% hardwood and 40% softwood was blended andmixed together in the Hollander Beater. Tap water was used to achievethe 5% consistency. Once the pulp was blended and re-hydrated withwater, the pulp slurry was transferred to a Back Chest and diluted to a1.5% by weight consistency with tap water. The pH of the slurry wasadjusted to 7.5 buy the addition of H₂SO₄. From the Back Chest, the pulpslurry was sent through a single disc Jordon refiner until a freeness of450 mL CSF was achieved. The freeness was determined by TAPPI TestMethod T-227. A load weight of 40 lbs and a flow rate of 60 gpm were theoperation parameters on the Jordon refiner. The refining time of eachbatch was kept constant (12 minutes). The EFA-C material was added tothe Back Chest prior to refining at a dosing level of 0.5% by weight.Once refining was completed, the pulp slurry was transferred to theMachine Chest and diluted to 0.5% by weight consistency.

Making Paper: Two different basis weight grades of paper were targeted,a 36 lb/3300 ft² and a 73 lb/3300 ft². Basis weights were achieved bycontrolling the machine speed. When called for during the experiment, 10lb/ton of cationic starch (Charge+110) was added at the Stuffbox. The0.5% (by weight) slurry was transferred from the Machine Chest to theHeadbox. From the Headbox, the slurry was transferred to the Fourdrinierwhere the first stages of dewatering took place. The wet paper webpassed through the Dandy roll and suction boxes where more water wasremoved from the web. The web proceeded to the Couch roll where it wastransferred to the felts and into the First Press Section. From theFirst Press section, the web was transferred to another set of feltsinto the second press section and from there into the First DryerSection. The Size Press and Second Dryer sections were by-passed. Thefinal stage of the web passed through the Calender Stack and onto to theReel.

Paper Testing All the paper testing was performed by Western MichiganUniversity-Paper Science & Engineering. Table 5 represents thereferences to the TAPPI Test Procedures and number of replicationsperformed on each test.

TABLE 5 TAPPI Test Methods Test Identification TAPPI Method ReplicationsBasis Weight T-410 om-93 5 Ash Content T-413-om-93 3 Bulk T-220 sp-9614.3.2 10 Gurley Porosity T-460 om-96 10 Caliper T-411 om-89 10 TensileStrength T-494 om-88 10 MD/10 CD Opacity T-425 om-91 5 Tearing ForceT-414 om-88 5 Scott Bond T-541 om-89 5 Burst Strength T-403 om-91 10wire side/10 felt side Gurley Stiffness T-543 om-94 5 MD/5 CD FoldingEndurance T-511 om-96 10 MD/10 CD Sheffield Roughness T-538 om-96 10wire side/10 felt side

Results: The paper testing results are shown in Table 6.

TABLE 6 Western Michigan University Pilot Paper Machine Trial ActualGurley Tensile Strength Grade B.W. Bulk Porosity Caliper (kN/m) ScottBond ID (lb/3300 ft²) (lb/3300 ft²) (cm³/g) (sec/100 mL) (mil) MD CD (ftlb/1000 in²) Control 36 24.9 2.79 3.04 3.36 1.99 1.17 157 EFA-C 36 26.92.58 3.90 3.37 3.06 1.24 162 Control 73 49.7 2.84 6.33 6.83 5.62 2.70143 EFA-C 73 51.6 2.61 7.74 6.54 6.19 3.02 159 Tensile Index FoldingEndurance Tearing Force Grade (N m/g) (log10 MIT) Opacity (gf) ID(lb/3300 ft²) MD CD MD CD (%) MD CD Control 36 6.19 3.64 1.62 0.90 76.1865 81 EFA-C 36 8.78 3.55 1.80 1.06 79.12 74 88 Control 73 8.75 4.20 2.171.48 88.26 157 167 EFA-C 73 9.27 4.51 2.33 1.49 88.52 173 185

FIG. 9 shows the Burst strength of the paper at two different basisweights made with and without the EFA-C. A statistically significantimprovement was to measured at the 36 lb sheet, but not at the 73 lbsheet.

FIG. 10 shows the Tensile strength of the paper at two different basisweights made with and without the EFA-C. A statistically significantimprovement in tensile strength was measured in the machine directionfor both 36 lb and 73 lb sheets, but only for the 73 lb sheet in thecross-machine direction.

FIG. 11 shows the Tear strength of the paper at two different basisweights made with and without the EFA-C. A statistically significantimprovement in tear strength was measured for both 36 lb and 73 lbsheets.

FIG. 12 represents the Scott Bond strength of the paper at two differentbasis weights made with and without the EFA-C. Statistically significantimprovement in Scott Bond occurred for both the 36 lb and 73 lb sheets.

FIG. 13 shows the Porosity of the paper at two different basis weightsmade with and without the EFA-C. Statistically significant improvementin porosity occurred for both the 36 lb and 73 lb sheets.

FIG. 14 shows the Bulk density of the paper at two different basisweights made with and without the EFA-C. Statistically significantimprovement in bulk density occurred for both the 36-lb and 73 lbsheets.

FIG. 15 shows the Fold Endurance strength of the paper at two differentbasis weights made with and without the EFA-C. Statistically significantimprovement occurred for both the 36 lb and 73 lb sheets, except for the73 lb sheet in the cross-machine direction.

Conclusions: The pilot paper machine trial at Western MichiganUniversity (WMU) statistically validated the laboratory observationsthat 0.5% of the EFA-C statistically enhanced the Burst and Tensilestrength paper properties. In addition, the pilot study alsostatistically validated the enhancement of the following paperproperties when 0.5% EFA-C was added to a standard hardwood-softwoodbleached papermaking furnish: Scott Bond, Tear, Fold, Porosity, andBulk.

Example 11 Papermaking: Pilot Investigation of EFA and Cationic Starch

A pilot paper machine trial was performed at Western Michigan Universityin the Paper Science & Engineering Department. The objective of thetrial was to determine if the paper strength enhancement properties ofthe EFA-C would be changed by the addition of cationic starch.

Papermaking Furnish Preparation: Hardwood and softwood bleached Kraftcommercially available market pulp was supplied by Western MichiganUniversity. Two different batches of a 60% hardwood and 40% softwoodfurnish were prepared for the study. One batch contained no EFA-C andwas labeled “Control.” The other batch contained 2.0% EFA-C and waslabeled “EFA-C” batch. Each batch was prepared as follows: A 5% byweight consistency of 60% hardwood and 40% softwood was blended andmixed together in the Hollander Beater. Tap water was used to achievethe 5% consistency. Once the pulp was blended and re-hydrated withwater, the pulp slurry was transferred to the Back Chest and diluted to1.5% with tap water. The pH of the slurry was adjusted to a pH of 7.5with H₂SO₄. From the Back Chest, the pulp slurry was sent through asingle disc Jordon refiner until a freeness of 450 mL CSF was achieved.The freeness was determined by TAPPI Test Method T-227. A load weight of40 lbs and flow rate of 60 gpm were the operation parameters assigned tothe Jordon refiner. The refining time of each batch was kept constant(12 minutes). The EFA-C material was added to the Back Chest prior torefining at a dosing level of 2.0% by weight of the EFA-C. Once refiningwas completed, the pulp slurry was transferred to the Machine Chest anddiluted to 0.5% consistency.

Making Paper: Two different basis weight grades of paper were targeted,a 36 lb/3300 ft² and a 73 lb/3300 ft². Basis weights were achieved bycontrolling the machine speed. When called for during the experiment, 10lb/ton of cationic starch (Charge+110) was added at the Stuffbox. The0.5% slurry was transferred from the Machine Chest to the Headbox. Fromthe Headbox the slurry was transferred to the Fourdrinier as describedpreviously. The Size Press and Second Dryer sections were by-passed asbefore. The final stage of the web passed through the Calender Stack andonto to the Reel.

Paper Testing: All the paper testing was performed by Western MichiganUniversity-Paper Science & Engineering. Table 7 represents thereferences to the TAPPI Test Procedures and number of replicationsperformed on each test.

TABLE 7 TAPPI Test Methods Test Identification TAPPI Method ReplicationsBasis Weight T-410 om-93 5 Ash Content T-413-om-93 3 Bulk T-220 sp-9614.3.2 10 Gurley Porosity T-460 om-96 10 Caliper T-411 om-89 10 TensileStrength T-494 om-88 10 MD/10 CD Opacity T-425 om-91 5 Tearing ForceT-414 om-88 5 Scott Bond T-541 om-89 5 Burst Strength T-403 om-91 10wire side/10 felt side Gurley Stiffness T-543 om-94 5 MD/5 CD FoldingEndurance T-511 om-96 10 MD/10 CD Sheffield Roughness T-538 om-96 10wire side/10 felt side

Results: The results of the paper testing are shown in Table 8.

TABLE 8 Western Michigan University Pilot Paper Machine Trial CationicActual Gurley Tensile Index Grade EFA-C Starch Basis Weight BulkPorosity Caliper (N m/g) (lb/3300 ft2) (%) (lb/ton) (lb/3300 ft²)(cm³/g) (sec/100 mL) (mils) MD CD 36 0 0 37.61 2.82 3.28 3.47 29 13 36 010 36.82 2.79 3.04 3.36 54 32 36 2 0 37.46 2.63 3.54 3.23 29 12 36 2 1037.27 2.69 4.10 3.29 37 15 73 0 0 69.63 2.78 6.02 6.34 58 31 73 0 1073.52 2.84 6.33 6.83 76 37 73 2 0 73.46 2.62 7.72 6.31 60 29 73 2 1072.41 2.71 8.52 6.18 78 37 Cationic Tearing Force Burst Index GradeEFA-C Starch Opacity (gf) Scott Bond (kPa g/m² ) (lb/3300 ft2) (%)(lb/ton) (%) MD CD (ft lb/1000 in²) Wire Felt 36 0 0 77 67 67 106 1.170.97 36 0 10 76 65 81 143 2.87 2.99 36 2 0 74 54 68 126 1.03 1.00 36 210 74 61 69 173 1.37 1.35 73 0 0 89 143 132 109 2.37 2.39 73 0 10 88 157167 157 3.01 3.29 73 2 0 86 126 128 126 2.45 2.30 73 2 10 85 136 143 1603.24 3.10 Cationic Gurley Stiffness Folding Endurance SheffieldRoughness Grade EFA-C Starch (gurley units) (log10 MIT) (mL/min)(lb/3300 ft2) (%) (lb/ton) MD CD MD CD Wire Felt 36 0 0 225 71 1.22 0.58202 230 36 0 10 204 98 1.62 0.90 192 230 36 2 0 215 68 1.12 0.54 177 20736 2 10 185 38 1.53 0.88 180 213 73 0 0 390 164 1.73 1.11 232 284 73 010 420 194 2.17 1.48 237 287 73 2 0 330 158 1.55 0.90 222 279 73 2 10376 165 1.99 1.29 223 264

FIG. 16 shows the enhancement of Scott Bond internal paper strength withthe addition of 2.0% EFA-C. An additional increase was measured when 10lb/ton of a cationic starch was added.

FIG. 17 shows the ability of EFA-C to make the sheet less porous.Porosity, as measured by the TAPPI test method Gurley Porosity, wasmeasured by the amount of time it takes to pass 100 mL of air through agiven area of the sheet. The longer it takes the air to pass through thesheet, the less porous the sheet. The higher the Gurley Porosity, thegreater the coating holdout.

FIG. 18 shows the densification of the paper with the addition of 2.0%EFA-C.

Conclusions: The addition of 2.0% EFA-C increased the internal bondstrength of paper as measured by the Scott Bond TAPPI test method. When2.0% EFA-C was incorporated into the paper, the sheet became lessporous. The Bulk density of the paper increased with the addition of2.0% EFA-C. Incorporation of a cationic starch with the 2.0% EFA-C intothe paper enhances the properties described above. The pilot papermachine study also indicated that there is a synergistic effect of usingthe EFA in conjunction with a cationic starch with respect to machinerunnability parameters of drainage and retention.

Example 12 Papermaking: Analysis of EFA-C in Paper Products

The objective of the study was to determine whether a test method couldbe developed which identified the EFA technology in a paper productusing either a microscopic and/or spectroscopic technique. Paper wasmade with different concentrations of EFA-C on the pilot paper machineat Western Michigan University Paper Science & Engineering Department.

Papermaking Furnish Preparation: Hardwood and softwood bleached Kraftcommercially available market pulp was supplied by Western MichiganUniversity. Different batches of a 60% hardwood and 40% softwood wereprepared for the study. Each batch contained one of the following levelsof EFA-C: 0%, 0.5%, 1.0%, and 2.0%. Each batch was prepared as follows:A 5% by weight consistency of 60% hardwood and 40% softwood was blendedand mixed together in the Hollander Beater. Tap water was used toachieve the 5% consistency. Once the pulp was blended and re-hydratedwith water, the pulp slurry was transferred to the Back Chest anddiluted to 1.5% with tap water. The pH of the slurry was adjusted to apH of 7.5 with H₂SO₄. From the Back Chest, all of the pulp slurry wassent through a single disc Jordon refiner three times. A freeness of 480mL CSF (TAPPI Test Method T-227) was measured. A load weight of 20 lbsand flow rate of 60 gpm were the operation parameters of the Jordonrefiner. The refining time of each batch was kept constant. The furnishwas drawn from the Back Chest through the single disc Jordon refiner andonto the Machine Chest. Once the Back Chest was drawn empty, the Jordonrefiner was turned off. The batch was then transferred from the MachineChest back to the Back Chest. This process was repeated three times foreach batch containing different levels of EFA-C. Once refining wascompleted, the pulp slurry was transferred to the Machine Chest anddiluted to 0.5% consistency.

Making Paper: Three different basis weight grades of paper were targetedat 20, 40, and 60 lb/3300 ft². Basis weights were achieved bycontrolling the machine speed. For runability purposes, 10 lb/ton ofcationic starch (Charge +110) was added at the Stuffbox. The 0.5% slurrywas transferred from the Machine Chest to the Headbox. From the Headboxthe slurry was transferred to the Fourdrinier as described previously.The Size Press and Second Dryer sections were by-passed as before. Thefinal stage of the web passed through the Calender Stack and onto to theReel.

Example 13 Paper Properties: Microscopic Examination

The paper samples from Example 12 were subjected to standard ScanningElectron Microscopy examination in order to determine if any structuralchanges were occurring as a result of the usage of the EFA-C in thepaper making process. FIG. 19 shows a SEM image at 800× of a 40 lb sheetmade in the manner described above. Note the small micro-fibrils thatconnect the fibers as well as the large void spaces as the fibers wereoverlaid to make the paper surface. The presence of micro-fibrils isknown to increase the strength of the paper sheet (T. E. Conners and S.Banerjee in Surface Analysis of Paper, CRC Press, 1995). FIG. 20 showsan SEM image at 800× of a 40 lb sheet made with 1% EFA added before therefining step. Note the increase in micro-fibril production in thisexample. Also note that the void spaces observed in FIG. 19 are nowreduced, indicating a better formation of the paper sheet.

In total, a 23% increase in micro-fibril production was noted in theabove paper sheets. Calculations were performed on 20 SEM field imagesof paper without EFA addition and 20 SEM field images of paper with 1%EFA-C addition. Paper without EFA averaged 13 micro-fibrils permicrograph field and paper with 1% EFA-C averaged 16.5 micro-fibrils permicrograph field, thus an increase of 23% over non-EFA paper.

Example 14 Paper Properties: Fourier Transform Infrared SpectralAnalysis

Infrared spectral analyses of paper handsheets were performed todetermine whether a method of detection of EFA usage in paper could bedeveloped. Fourier transform infrared reflectance spectra of 40-lb sheetwith no EFA-C added and of 40-lb sheet with 1% EFA-C were scanned. FIG.21 shows the results of the test. The top spectrum is from paper with noEFA-C added, the middle spectrum is paper with 1% additive, and thebottom spectrum is the residual after spectral subtraction using asimple 1:1 ratio factor. The region of most difference in the twospectra are circled in the figure.

Example 15 Paper Properties: Near Infrared Reflectance Analysis

While FTIR reflectance analysis is suitable for qualitative work, itless suitable for quantification, particularly in samples with high orvariable moisture content. Since the FTIR analysis shows that there areregions of difference, near Infrared reflectance analysis was used forquantification studies.

A set of paper handsheets were subjected to near infrared reflectanceanalysis. In total, six different handsheets sets were used, a 20 lb, 40lb, and 60 lb sheets with no EFA-C added, and a 20 lb, 40 lb, and 60 lbsheets with 1% EFA-C added. Representative samples were cut out ofmultiple handsheets and the near infrared reflectance spectra werescanned. Three regions of each paper were used, giving a total of 18samples that were analyzed.

FIG. 22 was generated using a simple correlation analysis a commonmethod for viewing near infrared data for quantitative analysis. Thesimple correlation coefficient (degree of linearity) at each wavelengthis given. This is useful in determining which wavelengths are moresuitable for developing a quantitative calibration model.

Note the two regions of highest correlation. If we apply a multiplelinear regression algorithm to the data, a linear relationship can bedeveloped using these two wavelengths. The linear relationship developedfrom this data has a correlation coefficient of 0.96 and a standarderror at 95% confidence of 0.14. This is definitive evidence that theEFA content in paper can be determined by independent analysis.

Example 16 Comparison of EFA-C to Commercially Available Fiber Additives

The EFA was compared with other commercially available sources ofinsoluble dietary fiber, including solka floc, microcrystallinecellulose, oat fiber, corn bran, and wheat bran. A comparison isprovided in Table 9.

TABLE 9 Comparison of EFA-C to Commercially- Available Insoluble FiberProducts Microcrystalline Solka Corn Wheat Oat EFA-C Cellulose Floc BranBran Fiber % TDF 87.2 93-97 100 81 38-50 93 (dry basis) % soluble 0 0-90 2 4 0 % insoluble 87.2 84-97 100 79 34-46 93

The total dietary fiber (TDF) content of the commercially-availableproducts ranged from about 81% to 100%, except wheat bran which containsonly 38-50% TDF. All of these products are used in food fortification asconcentrated sources of dietary fiber. The proximate analysis describedin Example 7 confirmed that EFA-C contains about 87.2% of insolubledietary fiber, comparable to other commercial fiber products.

Example 17 Functionality

It is common for food manufacturers to use a combination of insolubleand soluble fiber in food formulation. The insoluble fiber products areused largely for fortification, and the soluble fiber products forfunctionality. Basic functionality tests were conducted to assessviscosity building, water holding capacity, and oil holding capacity ofthe various products. The test protocols are described in Example 7.

Preliminary screening revealed that EFA has greater viscosity building,water holding capacity, and oil holding capacity than some othercommercially available insoluble fiber products includingmicrocrystalline cellulose, solka floc, and corn bran. The observedfunctionality of EFA suggests that it can provide improved organolepticproperties, such as mouthfeel, plus desirable product properties such asemulsion stabilization, cling, clouding, anti-staling, freeze/thawstability, and cook yield in foods. The results of the functionalitytests are summarized in Table 10.

TABLE 10 Functionality Screening of Several Insoluble Fiber ProductsWater Oil 24 Hour Viscosities (cP) Capacity capacity Stirred ShearedHomogenized %* % @ EFA-C 10 20 440  550 b 300 b Avicel CL- 130 130 130 480 c  80 g 611F Avicel RC- 212 1,330 680 1360 a  80 g 581F Avicel FD-<10 <10 <10  180 f 100 e 100 Solka Floc <10 <10 <10  530 bc 340 a 40 FCCSolka Floc <10 <10 <10  350 d 220 c 200 FCC Solka Floc <10 <10 <10  310d 200 d 300 FCC Corn Bran <10 <10 <10  210 d, f 100 e Ultra Corn Bran<10 <10 <10  170 e 100 e Fine Corn Bran <10 <10 <10  250 e  95 e Medium*values with the same letter are not significantly different at the 95%confidence limit. @ values with the same letter are not significantlydifferent at the 95% confidence limit.

Example 18 Viscosity Building

Samples were prepared for viscosity building analysis by dispersing 3 gof fiber into 200 g of deionized water using one of the following threeprocedures:

-   -   1. stirring for one minute on magnetic stir plate (“stirred”)    -   2. shearing on high speed in a Warring blender for 1 minute        (“sheared”)    -   3. single pass homogenization at 5000 psi in a Gaulin        Homogenizer (“homogenized”).

The viscosities of the samples, in 250 mL beakers, were measured after24 hours at room temperature using a Brookfield RV viscometer, Spindle#2 at 20 rpm.

Two of the Avicel MCC products showed the greatest viscosity buildingability of all the fibers. Avicel RC581F reached over 1000 cP and AvicelCL-611F reached 130 cP with high shear. However, these products alsocontain 59% carboxymethylcellulose (CMC) which is a soluble fiber thatcould be responsible for the viscosity building. These samples appearedmilky white, opaque suspensions that precipitated slightly after 24hours. Avicel FD-100, solka floc and corn bran, which contain no solublefiber, did not build viscosity under any of the mixing/shearingconditions and rapidly precipitated to the bottom of the beaker.

The viscosity of EFA-C reached more than 400 cP with homogenization andhad a white, translucent, suspended flocked appearance that did notprecipitate out of solution. This is a good functionality for a purelyinsoluble fiber product. Due to the viscosity building characteristic ofEFA, it is suitable for use in nutrition beverages to impart a thick,creamy mouthfeel, to help suspend fine solids like cocoa powder andminerals, and to help stabilize the emulsion. The flocked appearance ofthe additive resembles fruit pulp. Thus, the additive can be used as aclouding agent in juice drinks or sport beverages.

Example 19 Food Application Example of Water Holding Properties of EFA

The ability of EFA to bind up to 5 times its weight in water leads tosignificant improvements in the shelf life of bakery products and anopportunity to enrich such products with low to moderate levels ofinsoluble fiber.

Five home made breads were prepared with the following ingredients inthis Example:

Bread flour 40.8 Water 23.1 Whole wheat flour 13.0 Egg 8.9 Honey 7.9Nonfat Dry Milk 1.9 Unsalted Butter 1.4 Salt 1.2 Lemon juice 0.9 Activedry yeast 0.9 100%

The yeast was dissolved in water and set aside. Wet ingredients werecombined and added to the dry ingredients and mixed for 1 minute using aHobart mixer and dough hook. Dough was allowed to rise twice before itwas baked at 375° F. for 50 minutes

To Sample A, 1% EFA (flour basis) was added to the bread mix. Samples B,C and D contained 3%, 5% and 7% EFA (flour basis), respectively, Thefifth sample contained no EFA and served as the control. No additionalwater or other ingredients were added to the formulations, nor wereprocessing changes made for any of the breads. Final products wereanalyzed by Medallion Laboratories for percent moisture and soluble,insoluble and total dietary fiber. Results were as follows:

% Total % Insoluble % Soluble % Moisture Dietary Fiber Dietary FiberDietary Fiber Control 33.2 3.9 2.9 1.0 Sample A 33.0 4.3 3.3 1.0 SampleB 34.0 5.1 4.2 0.9 Sample C 33.6 5.7 4.6 1.1 Sample D 34.4 5.8 5.5 0.3

As can be seen in the table above, the moisture levels were higher inbread containing 3-7% EFA. The data also show it is possible tomoderately increase the insoluble fiber content of breads by adding arelatively small amount of EFA. A similar observation was seen in yellowcake and soft-type oatmeal cookies.

To further illustrate the water binding properties of EFA, batters wereprepared with the following ingredients in Example 2:

Milk 52.3 Flour 35.2 Egg 11.4 Baking powder 0.9 Salt 0.2 100%

Sample A contained 1% of EFA, sample B contained 1.5% EFA, and Sample Ccontained 2% EFA on a total batter weight basis. Batters were mixedtogether until smooth and allowed to rest for 10 minutes. Onions,mushrooms, zucchini and chicken were coated with batter and deep fatfried in liquid vegetable oil at 375° F. for 4 minutes. The friedproducts were removed from the hot oil and placed on paper towels tocool. The fried batter was then removed and analyzed for percent fat(acid hydrolysis) and percent moisture (vacuum oven). Results formushrooms and zucchini are shown in FIGS. 28 and 29.

Since EFA is more hydrophilic than lipophilic, a reduction in the fatcontent of fried food products containing EFA was seen. Moreover, EFAaddition may provide additional strength to fried products due to itsfibrous nature, resulting in less breakage during flying and shipping.

Example 20 Food Application Example Utilizing Oil Holding Properties ofEFA

Since EFA is capable of binding up to 3 times its weight in fat and 5times its weight in water, the addition of EFA to processed meatproducts leads to direct increases in cooking yield and improvements inthe moisture and fat contents of such products when EFA is present atlevels of 1% to 3% based on the total weight of the meat mixture.

Four samples using 80% lean ground check with no additives orpreservatives were used as the basis for the tests conducted in thisExample. To Sample A, exactly 1% (w/w) ground EFA was added to 500 gramsof ground chuck. Similarly, 2% and 3% (w/w) ground EFA was added toground chuck Samples B and C, respectively. The fourth sample containedno added EFA, and served as the control. All sample mixtures wereblended on low speed using a Hobart mixer with paddle attachment for 10minutes to ensure that each sample was well mixed. No additional wateror other ingredients were added to the mixtures. The meat mixtures werethen formed into 125 gram patties. The patties were kept in cold storageto ensure that all samples would have the same initial cookingtemperature. Four meat patties of each type were fried at 350° F. for 6minutes on each side. The fried patties were placed on wire racks andallowed to cool to room temperature prior to weighing each patty todetermine the change in cooking yield. The samples were also analyzedfor moisture (AOAC method 960.39) and fat (AOAC method 950.46). Theresults of the analyses are shown below.

% Decrease in Cook Yield % Fat % Moisture Control 38.3 18.0 51.8 SampleA 33.9 18.4 53.8 Sample B 29.8 18.3 54.0 Sample C 29.7 18.8 54.2

As can be seen in the above results, the addition of EFA to ground chuckled to improvements in cooking yield. The addition of EFA also increasedthe lipid and moisture content of the patties. Moreover, all meatpatties that contained EFA appeared more juicy and appealing than thecontrol.

VI. Mode of Action of the Enhanced Fiber Additive in Paper Production

As indicated by Examples 8 and 9, it has been found that a 40 pound(40#) handsheet with 0.5% EFA retains the same tensile and burststrength as a 60 pound (60#) handsheet without any EFA; and, thus, 0.5%enhanced corn fiber (EFA-C) has the potential to replace 33% of the woodfiber in a standard 60# sheet without loss of strength, at the same CSF.Thus, the EFA material has a significant potential as a high value addedpaper additive product. In this section, analysis is made of thepossible mode of action of the strength enhancement properties of theEFA material and its possible interactions with the paper fiber.

VI. A. Surface Properties

FIG. 23 shows a Scanning Electron Micrograph (SEM) image of paperenhanced with EFA and paper without EFA. All of the papers in this studywere generated during a pilot paper machine trial at Western MichiganUniversity, as characterized above in connection with Example 10. Atfirst glance at 100× magnification, there is no apparent difference insurface morphology.

However, under more intense magnification, a striking property emerges.This was discussed above in connection with Example 13, and is apparentby comparison of FIGS. 19 and 20. FIG. 19 shows an 800× magnificationSEM of non-EFA paper. Micro-fibrils that join the larger fiberstogether, are observed. Such fibers are well known and documented inpaper manufacturing processes and are attributed to strength buildingproperties. These microfibrils are laid down during sheet formation,thus increasing hydrogen bonding effects.

FIG. 20 shows the SEM image of the 1% EFA enhanced paper. There is anobservable increase in microfibril formation. To determine if theformation is a consistent effect, multiple SEM fields and multiplesheets of paper were imaged and the microfibrils counted. The papersmade with the EFA material had a microfibril production increase of morethan 10% (typically >15%, for example, about 23%) over the non-EFApapers. It is reasonable to conclude that this increase in microfibrilproduction plays a significant role in the strength enhancing propertiesof the EFA, generally by providing a bridging network of microfibrilsbetween larger pulp (cellulose) fibers.

VI. B. Depth Properties

While SEM is a powerful surface technique, it is limited in its abilityto determine structural details, particularly details that are notvisible on the surface. Another technique for paper analysis is LaserConfocal Scanning Microscopy (CLSM or LCSM). This technique not onlyallows the viewing of surface details, but it can also scan into thematerial in the Z direction to reconstruct three-dimensionalrepresentations of the structure.

An experiment was conducted to generate LCSM fluorescence images ofpaper with no EFA and paper with 1% EFA. Two excitation wavelengths wereused. The first was from a 542-nanometer laser, and the second was froma 488-nanometer laser. By combining the two images, a composite imagewas generated. Different colors were used to present the imaging fromthe different nanometer lasers. Up to 20 Z series slices were taken andthen added to the composites to enhance the depth of field.

When the morphological differences in the pictures were examined, nostriking features appeared. Both the EFA and the non-EFA paper wereobserved to have similar structural features, fiber packing anddensities. That is, the gross morphology of the EFA and the non-EFApaper were so similar as to be undetectable by this type of observation.This is significant for many paper applications, since it indicates thatthe EFA additive will likely not cause significant gross structuralchanges in the paper, although as indicated above, it will causemodifications in microfibril effect. Indeed, as will be apparent fromthe discussions in the next section, a reason that gross morphologicaldifferences are not observed is because the EFA operates by partiallycoating the cellulose fibers of the paper (i.e., aligning with the largecellulose fibers), and then, due in part to the hemicellulose content ofthe EFA, forming bridging microfibrils.

VI. C. Chemical Detection

While undetectable morphological features are a positive observationwith respect to assessing whether the EFA additive causes anysignificant morphological changes in the paper, chemical detection ofEFA in paper is important to understanding its chemical interactions, aswell as providing a mechanism for determining the presence of, andlocation of, EFA additive in papers.

Spectroscopic examination of the paper material provides a means ofdetermining the chemical differences and similarities of EFA and non-EFApaper. As discussed in connection with Example 14, FIG. 21 shows FURreflectance spectra of paper: (a) with EFA additive; (b) without EFAadditive; and, (c) at the bottom line of FIG. 21, differences betweenthe two spectra. In one region indicated in the bottom line, the twospectra are quite different. This is the 1200-1300 cm⁻¹ region. Thedifferences appear are due to chemical differences, not merely grossreflectance difference.

In the bottom line of FIG. 21, which depicts the differences, note themajor bands of difference at 1137 cm⁻¹ and 1220 cm⁻¹. These differencescan be used in various ways. For example:

-   -   1. By using these wavelengths in conjunction with a chemical        imaging system, a chemical mapping of the EFA distribution in        the paper can be generated; and    -   2. A quantitative analytical method can be developed to directly        measure the EFA content of the manufactured paper.

VI. D. Chemical Imaging

Chemical imaging is a technology that can be used to visualize chemicalcomposition interactions in materials. Both Raman and Infrared imagingsystems are available. Since paper samples tend to have highfluorescence backgrounds (hence the ability to perform CLSM), Ramanimaging is not practical. However, infrared imaging can provide a verydetailed map of the chemical morphology of the surface.

FIG. 24 shows an infrared chemical image taken of EFA paper. The imageswere generated by using a chemometric technique called principalcomponent analysis (PCA). This type of technique enhances the chemicaldifferences found in the “principal components” of the variations in thematerial examined. The image shown in FIG. 24 is of the third principalcomponent of the paper image. In chemical imaging the contrast generatedin the image are from chemical, rather than morphological, differences.The measurements used, and imaging analysis, were performed by Chemlcon,Inc. at Pittsburgh, Pa., using that company's facilities and software,under the supervision of Cargill, Inc., the assignee of the presentapplication.

The image of the EFA added paper (FIG. 24) shows marked contrasts. Thatis, there are localized chemical differences across this image. In fact,on close examination of the EFA image, one can see that the chemicalchanges generated by the presence of the EFA material is localized orordered to follow (or to align and define) individual paper (in thiscase pulp or cellulose) fiber strands. That is, the EFA is located suchthat it coats, or at least partially coats, various paper fibers (i.e.,cellulose or pulp fibers in this instance). Since the EFA material has asignificant holocellulose character, it readily interacts with the wood(cellulose) fibers. Because of its hemicellulose character, the EFA actsas “glue” in paper manufacturing. Thus, it can be concluded that the EFAadditive effectively coats (or partially coats) each paper(holocellulose) fiber with a thin film of hemicellulosic “glue” and inthis manner add to the overall strength of the paper.

In order to ensure that the PCA 3 image contrast is from EFA, a smallpiece of ground EFA material was placed upon the paper and imaged inprincipal component space.

It is noted that when the experiment was performed, and the differenceswere plotted by the researchers, the chemical differences were plottedin color, to enhance contrast in the image generated. A black and whiteimage is provided in the current to figures.

VI. E. Quantitative Analysis

Once it was observed that EFA could be detected spectrally, and evenimaged spectrally, it was concluded that a quantitative spectral modelcould be developed. Such a model would enable one to determine not onlyif EFA material were present in the paper, but to determine how much EFAis present.

A calibration data set was put together with 0% and 1% EFA additive todemonstrate that a quantitative spectra model could be developed. Byrecording the reflectance near infrared spectrum of each paper sample, aspectra correlation plot was developed.

FIG. 22, discussed in Example 15 above, shows the correlation plotgenerated. Note the two areas of highest correlation with EFA. These twowavelengths directly correlate to the third overtones of the fundamentalbands of difference in the FTIR spectral subtraction (from FIG. 21).

Taking this near infrared data and using a multiple linear regressionalgorithm, a linear relationship was discovered using the twowavelengths. FIG. 25 shows the linear plot generated from thiscalculation.

VI. F. Conclusions

The following conclusions can be made about the paper application ofEFA, based upon the above experiments and analysis:

-   -   1. The paper enhancements of EFA occur with very little        differences occurring visually (SEM at 800×) in bulk structure        between paper with and without EFA.    -   2. A statistically valid link exists between microfibril        production and EFA content. This effect at least partially        contributes to the strength building characteristics of EFA.    -   3. Differences in infrared spectra characteristics are        observable, showing that there are chemical differences between        EFA and cellulose.    -   4. Differences in FTIR spectra are real as overtones of these        bands are present in NIR correlation analysis.    -   5. NIR imaging graphically shows EFA localized chemical        differences from EFA addition, in the form of “coating” of the        paper (cellulose) fibers. This effect contributes to the        strength building characteristics of EFA.    -   6. The spectral differences are large enough to develop an        analytical method for EFA in paper using NIR.

VII. Chemical Affinity Probes

Another useful evaluative tool with respect to evaluating EFAcharacteristics, is chemical affinity probes. Specifically, there areenzyme affinity probes which can be used with transmission electronmicroscopy (TEM) imaging.

More generally, cytochemical affinity probes can be used to distinguishchemical properties in samples. In particular, a cellulase-gold affinityprobe binds selectively to cellulosic material and not cutin and otherhydrophobic material.

A reasonable premise for such an investigation is that binding of anaffinity gold probe to substrate on the section surface is affected bythe hydrophilicity of the wall. This is supported by the observationthat walls containing suberin or cutin do not label with cellulase-gold,even though they do contain cellulose. On the other hand, lignifiedwalls such those of xylem elements do label with cellulase-gold. Giventhe information that the preferred treatment to convert SBF to EFA canremove or modify lignin presence and affect fiber hydrophilicity, a testwas conducted to evaluate whether there is a difference detectable bybinding using a cellulase-gold probe.

In FIG. 26, a digital image of an SBF-Corn sample evaluated by acellulose-Corn gold affinity probe is depicted. In FIG. 27, a digitalimage of an EFA-Corn sample similarly treated, is depicted. The higherdensity of the probe in FIG. 27 indicates that the EFA has been modifiedin a manner making it more susceptible to the probe. It is theorizedthat this results from the material being modified to have a greater,more accessible, cellulose and helocellulose character. This issupported by the analysis in Section VIII.

VIII. The Determination of Simple Monosaccharides in LignocellulosicMaterials (i.e., SBF and EFA) by High Performance Anion ExchangeChromatography with Pulsed Amperometric Detection (HPAE-PAD)

The approach characterized in this section can be used to separate andquantify the monosaccharides commonly found in the lignocellulosiccomponents of plants. These components include, but are not limited toarabinan, galactan, glucan, xylan and mannan components. The methodinvolves hydrolysis of the lignocellulosic material with sulfuric acid,followed by direct analysis of the resulting monosaccharides by HighPerformance Anion Exchange Chromatography with Pulsed AmperometricDetection (HPAE-PAD). This method is an adaptation of procedurespublished previously in the literature. See K. A. Garlab, L. D.Bourquin, G. C. Fahey, Jr., J. Agric. Food Chem., 37, 1287-1293, 1989;and M. W. Davis, J. Wood Chem. Technol, 18(2), 235-252, 1998. Thecomplete disclosure of both of these references being incorporatedherein by reference.

Materials

Sodium Hydroxide, 50% (w/w), and concentrated sulfuric acid werepurchased from Fisher Scientific. Deionized water (>18 MΩ-cm) wasobtained from a Barnstead/Thermolyne NANOpure Infinity waterpurification system. D-arabinose, D-galactose, D-glucose, D-xylose andD-mannose were purchased from Sigma Chemical Co. All carbohydrateswere >99% in purity.

Sample and Standard Preparation

Each sample was dried and milled to pass through a 40-mesh screen. Themoisture of each sample was determined using an NIR moisture balance setat 130° C. Samples were hydrolyzed according to TAPPI method T249 cm-85,Tappi Test Methods, Tappi Press, Atlanta, Ga., 1985. (The completedisclosure of this Tappi method being incorporated herein by reference).To summarize, 40-60 milligrams of sample was weighed into a glass testtube. To the material in the tube, exactly 1 ml of 72% sulfuric acid wasadded. The samples were held in a water bath for 1 hr at 30° C., withoccasional stirring using a glass stir rod to facilitate dissolution ofthe sample material. Hydrolyzates were then diluted to 4% (w/w) sulfuricacid with deionized water and placed in an autoclave at 103±7 kPa for 60minutes. After hydrolysis, samples were diluted to 1000 ml in avolumetric flask and filtered through a 0.45 micron nylon syringe filterprior to injection. Standard solutions were hydrolyzed in the samemanner as the samples.

Chromatographic Conditions

Carbohydrates were separated and quantitated using High PerformanceAnion Exchange Chromatography with Pulsed Amperometric Detection(HPAE-PAD). The DX-500 chromatography system (Dionex Corporation,Sunnyvale, Calif.) consisted of gradient pump (model GP50), anautosampler (model AS-50) equipped with a Rheodyne injection valve, andan electrochemical detector (model ED-40) with Pulsed AmperometricDetection equipped with a combination pH-Ag/AgCl reference electrode. ACarboPac PA-1 analytical column (250 mm×4 mm i.d.) and guard column (50mm×4 mm i.d.) were used to separate the carbohydrates. The pulsedamperometric waveform settings E1, E2, E3 and E4 were set at +0.1, −2.0,+0.6 and −0.1 V for durations of 400, 10, 30 and 60 msec, respectively,for a total of 500 msec, in accord with published Dionex Technical Note21, incorporated hereby reference. Eluents were prepared using filtered,degassed and deionized high purity water and stored under pressurizedHelium. To clean the column, 100 mM NaOH was pumped at 1 ml/min for 10minutes, deionized water was pumped at 1 ml/min for 10 mM toreequillibrate the column, and the carbohydrates were eluted by pumpingdeionized water at 1 ml/min for 40 minutes. To stabilize the baselineand optimize detector sensitivity, 300 mM NaOH was added postcolumn at0.6 ml/min., in accord with, Dionex Technical Note 20, incorporatedherein by reference. The total run time per sample was 60 minutes.

Results

Response factors (RF) for each monosaccharide were determined bydividing the peak area of each carbohydrate by its correspondingconcentration. Analyte concentrations are based on the dry weight of thesample material and reported to the nearest 0.1% as the average of twoduplicate determinations using external calculation techniques. Allconcentrations are based on the anhydrous weight equivalent of eachcarbohydrate, e.g., 0.88 for arabinose and xylose, and 0.90 forgalactose, glucose and mannose. The % figure are reported as a % oftotal carbohydrate material in the sample.

1. Seed Based Fiber (SBF) Control—(i.e., not processed as describedherein.)

Holocellulose Hemicellulose Arabinan Galactan Glucan Xylan Mannan TotalTotal Corn¹ 14.1-17.0 4.0-5.0 20.5-29.0 24.2-31.1 0.6-0.9 68.1-77.543.1-53.0 (SBF-C) Soy² 5.3 3.7 39.1 8.8 6.9 63.8 24.7 (SBF-S) Oats³3.3-3.7 1.2-1.3 33.0-35.2 29.1-33.0 0.1 66.7-73.3 33.7-38.1 (SBF-O) ¹Thereported results are from analyses of six samples. ²The reported resultsare from an analysis of one sample. ³The reported results are fromanalyses of two samples.2. Enhanced Fiber Additive (EFA)—(i.e., processed generally according toExamples 1-3)

(%) Holocellulose Hemicellulose Arabinan Galacton Glucan Xylan MannanTotal Total Corn⁴ 0.2-0.4 0.7-0.9 64.5-80.9 5.3-6.4 1.6-2.0 73.3-89.08.1-9.2 (EFA-C) Soy⁵ 1.2-1.8 1.1-1.4 58.4-63.2 11.3-12.5 3.4-6.276.9-83.6 18.5-20.4 (EFA-S) Oats⁶ 0.6-0.8 0.1 68.9-74.3 11.3-15.2 0.185.1-86.4 12.1-16.2 (EFA-O) ⁴The reported results are based on analysesof seven samples. ⁵The reported results are based on analyses of foursamples. ⁶The reported results are based on analyses of two samples.

General Observations Regarding the Analysis

In general, the above characterized analysis is usable to identify anddistinguish preferred EFA materials from mere SBF materials, whenprocessed according to the techniques described herein. In particular,herein the arabinan, galactan, glucan, xylan and mannan percents, whenevaluated according to the process described and summed, will beconsidered to identify the “holocellulose factor” or “holocellulosecharacter” of a sample. This factor in generally relates to the totalamount of the carbohydrates in the sample which can be correlated toeither a hemicellulose or cellulose presence. This is because themonosaccharide values indicated are reflective of the components ofcellulose and hemicellulose.

The value obtained for the glucan analysis will be generallycharacterized herein as the “cellulose factor” or “cellulose character”.This is because the glucose monosaccharide that most closely correlatesto the presence of cellulose.

The sum of the arabinan, galactan, xylan, and mannan presence will bereferred to herein as the “hemicellulose factor” or “hemicellulosecharacter”. This is because the monosaccharides indicated generallycorrelate to the presence of hemicellulose in the sample evaluated.

It is not meant to be suggested by the above that the precise percentageof cellulose in the sample or the precise percentage of hemicellulose,specifically correlates to the measured factors. Rather the factors aregenerally indicative of the relative amounts of these materials present,to one another, and also relative to other carbohydrates that can befound in the sample.

For the experiments indicated above, comparisons can be made betweenmaterial which has and has not been treated through an acid treatment,acid chlorite treatment and peroxide treatment, in accord with theprinciples described herein (See Examples 1-3). In particular, seedbased fiber-corn (or SBF-C) is generally a material which has not beenacid, acid chlorite or peroxide treated. Enhanced fiber additive-corn(or EFA-C) is the same material, but after treatment in accord with theprinciples herein, i.e., in general according to Examples 1-3. Similarlyin this experiment SBF-Soy was compared to EFA-Soy and SBF-Oats wascompared to EFA-Oats.

Certain general observations are readily apparent from the experiment.For example:

1. Conversion from SBF to EFA generally results in an observableincrease in measured cellulose factor, as a percentage.

2. SBF materials generally exhibit a total cellulose factor no greaterthan 45%, typically 20-40%; whereas EFA materials exhibit a totalcellulose factor of at least 50%, typically 50-85 percent.

3. SBF materials generally exhibit a hemicellulose factor which ishigher than related EFA materials. (By “related” in this context it ismeant the same sample but after treated in accord with the processesdescribed herein (Examples 1-3) to convert the sample to EFA).

4. SBF materials generally indicate a total hemicellulose factor ofgreater than 23%, whereas EFA materials generally indicate a totalhemicellulose factor of at least 5% but no more than 23%, typically nogreater than 21%.

5. Processing convert SBF to EFA generally increases the totalmeasurable holocellulose factor, as a percentage.

6. With respect to corn, the total cellulose character of SBF-C istypically less than 30%, whereas as the total cellulose character forEFA-C is typically at least 60%, i.e., 64-81%.

7. For corn, the total hemicellulose character for SBF-C is typically atleast 40%, i.e., 43-53%, whereas for EFA-C the total hemicellulosecharacter is typically no less than 5%; and typically not more than 15%;i.e., 8-9.2%.

8. For corn, the total holocellulose character for SBF-C is typically inthe range of 68-78%, whereas for EFA-C, the total holocellulosecharacter is typically in the range of 73-90%.

9. For SBF-Soy, the typical holocellulose character is below 70%, forexample 63.8%, whereas for EFA-Soy, the total holocellulose content istypically at least 70%, for example, 75-85%.

10. For EFA-Soy, a hemicellulose content of no less than 5% is typicallyfound; for example 18.5-20.4%.

11. For soy, the process of converting the SBF to EFA, typically resultsin a measured total cellulose character that is increased; for example,SBF-soy typically has a total cellulose character in the range of35-45%, whereas EFA-Soy typically has a total cellulose character of atleast 50%, typically within the range of 55-65%.

12. For oats, the SBF-Oats generally exhibits a total cellulosecharacter of less than 40%, typically 30-36%, whereas the EFA oats(EFA-O) typically exhibit a total cellulose character of at least 60%,typically 65-75%.

13. For oats, the process of converting from SBF to EFA generally leadsto a reduction in the total hemicellulose character.

14. For SBF-Oats, the total hemicellulose character is typically greaterthan 25%, i.e., 30-40%, whereas for EFA oats the total hemicellulosecharacter is no less than 5% and typically is no more than 20%, i.e.,10-17%.

15. For oat fiber, the process of converting the SBF oat fiber to theEFA oat fiber leads to a total holocellulose character increase.Typically SBF-Oats has a total holocellulose character of 65-75%,whereas EFA oats typically has a total holocellulose character of atleast 80%, typically 84-88%.

When the above observations are furthered considered, certain patternsemerge, for example:

A. Typically, for EFA relative to SBF, the ratio of the total cellulosefactor to the total hemicellulose factor is increased. That is, theprocess of converting a SBF fiber material to EFA fiber material isprocessing which generates a total cellulose character/totalhemicellulose character ratio which increased, while at the same timeleaving a hemicellulose character of at least 5%. Typically a ratio ofat least 2:1 is reached.

1. For corn the ratio increased from less than 1:1 to at least 5:1,typically at least 7:1.

2. For soy the ratio increased from about 1.5:1 to at least 2:1;typically at least 2.5:1.

3. For oats the ratio increased from about 1:1 to at least 4:1.

B. As a percentage to the total holocellulose character, the totalhemicellulose character generally decreases with a processing of SBF toEFA.

1. For corn, the ratio of total hemicellulose character to totalholocellulose character decreased from a figure for SBF of greater than0.5:1 (typically 0.6:1 or larger) to a figure that was typically no morethan 0.2:1.

2. For soy, the ratio decreased from a figure that was greater than0.3:1 to a figure that was typically no more than 0.3:1.

3. For oats, the ratio decreased from a figure that was typically atleast 0.45:1 to a figure that was no more than 0.3:1, typically 0.2:1 orless.

C. The process of converting from a SBF to EFA, in accord with thepresent principles, generally provides corresponding increases the totalcellulose character and the ratio of total cellulose character to totalholocellulose character. For example:

1. For corn, SBF-C typically exhibits a ratio of total cellulosecharacter to total holocellulose character of no greater than about0.5:1, whereas EFA corn exhibits a total cellulose character to totalholocellulose character which is typically at least 0.7:1.

2. For soy, the ratio of total cellulose character to totalholocellulose character for SBF was no greater than about 0.65:1,whereas for EFA soy, the figure was typically no less than about 0.69:1.

3. For oats the ratio of total cellulose character to totalholocellulose character, in SBF-O, is typically no greater than about0.6:1, whereas for EFA-oats the ratio of total cellulose character tototal holocellulose character is typically no less than about 0.75:1.

IX. Other Modifications to SBF in Forming EFA

Processing prior to formation of EFA may be conducted to achievereduction in natural oil levels present in the fibers. One method toremove these natural oils would be by Soxlet extraction. The Soxletextraction thimble can be charged with SBF material and solvents addedto the reservoir and refluxing initiated. Over a 24-hour period, naturaloils soluble to the solvent of choice, can be extracted into the solventfraction. In a procedure used to remove different polarity oils, aseries of extractions on the same SBF material can be performed. Forinstance, a non-polar solvent such as pentane or hexane can be used toremove non-polar oils. After extraction for 24 hours, the pentane orhexane fraction would be removed and the Soxlet charged with a morepolar solvent such as dichloromethane. After a 24-hour period, thissolvent would be removed and be replaced with a more polar solvent suchas methanol. After a 24-hour extraction process this solvent is removedand the SBF material is allowed to dry. The three solvent fractions areevaporated to render fractionated oils specific to the particularsolvent system. The SBF material can then be utilized in the process formanufacturing EFA without the contamination from residual natural oils.

Also, because of its hydrophilic and hydrophobic nature, the EFA can beenhanced or fortified with additives, prior to use. For example, it canbe bound with a nutraceutical.

It is anticipated that in some instances, additional modifications tothe SBF used for forming the EFA, or to the EFA after formation, may bedesirable. For example, processing prior to formation of EFA may involvereduction in natural oil levels present in the fibers. Alternatively,the oil levels can be reduced after EFA formation.

1-40. (canceled)
 41. A food product comprising: flour; and at least 0.5%of an acid treated seed based fiber material, by wt. of flour present ina mix from which the food product is formed, the acid treated seed basedfiber material having a total cellulose character of at least 50%, atotal hemicellulose character of at least 5%, and a reduced lignincontent when compared to non-acid treated seed based fiber, wherein saidacid treated seed based fiber material has been treated at a temperaturebetween 110° C. and 140° C. for approximately 30 minutes toapproximately 60 minutes.
 42. A food product according to claim 41comprising: a. at least 3% of the acid treated seed based fibermaterial, by wt, of flour present in a mix from which the food productis formed.
 43. A food composition comprising: a. at least 0.5% by wt.,on the basis of total ingredients, unprocessed, of acid treated seedbased fiber material having a total cellulose character or at least 50%.44. A food composition comprising an acid treated seed based fibermaterial having a total cellulose character of at least 50%, a totalhemicellulose character of at least 5%, and a reduced lignin contentwhen compared to non-acid treated seed based fiber, wherein said acidtreated seed based fiber material has been treated at a temperaturebetween approximately 110° C. and approximately 140° C. forapproximately 30 minutes to approximately 60 minutes.
 45. The foodcomposition according to claim 44, wherein the acid treated seed basedfiber material has a ratio of cellulose character to hemicellulosecharacter of at least 2:1.
 46. The food composition according to claim44, wherein the acid treated seed based fiber material comprises acidtreated corn fiber having a total cellulose character of at least 60%.47. The food composition according to claim 46, wherein the acid treatedcorn fiber has it ratio of cellulose character to hemicellulosecharacter of at least 5:1.
 48. The food composition according to claim44, wherein the acid treated seed based fiber material comprises acidtreated soy fiber.
 49. The food composition according to claim 48,wherein the acid treated soy fiber material has a ratio of cellulosecharacter to hemicellulose character of at least 2:1.
 50. The foodcomposition according to claim 44, wherein the acid treated seed basedfiber material comprises acid treated oat fiber having a total cellulosecharacter of at least 60%.
 51. The food composition according to claim50, wherein the acid treated oat fiber has a ratio of cellulosecharacter to hemicellulose character of at least 4:1.
 52. The foodcomposition according to claim 44, wherein the acid treated seed basedfiber material is selected from the group consisting of acid treatedcorn fiber, acid treated oat fiber, acid treated soy fiber, and mixturesthereof.
 53. The food composition according to claim 44, wherein theacid treated seed based fiber material is produced by a processcomprising treating a seed based fiber with an acid solution comprisingabout 0.001% to about 5% acid, based on the dry weight of the seed basedfiber.
 54. The food composition according to claim 53, wherein theresultant acid treated seed based fiber is further treated with aperoxide.
 55. The food composition according to claim 44, wherein theacid treated seed based fiber is present in an amount of at least about0.5% based on the total weight of the food composition.
 56. The foodcomposition according to claim 55, wherein the acid treated seed basedfiber is present in an amount ranging from about 0.5% to about 7%. 57.The food composition according to claim 44, wherein the thud is selectedfrom the group consisting of a beverage, a dressing, a sauce, a filling,a batter, a dry mix, a bakery product, a baked good, a frozen foodproduct a meat, a flour containing food product, and mixtures thereof.58. The food composition according to claim 57, wherein the food is aflour containing food product.
 59. A method of preparing a foodcomposition comprising incorporating in a food, an acid treated seedbased fiber. having a total cellulose character of at least 50%, a totalhemicellulose character of at least 5%, and a reduced lignin contentwhen compared to non-acid treated seed based fiber; wherein the acidtreated seed based fiber was acid treated at a temperature of at least110° C. for approximately 30 minutes to approximately 60 minutes. 60.The method according to claim 59, wherein the acid treated seed basedfiber is prepared by treating a seed based fiber with an acid solutioncomprising about 0.001% to about 5% acid, based on the dry weight of theseed based fiber.